EP2197794B1 - Crystallised material with hierarchised porosity and containing silicon - Google Patents
Crystallised material with hierarchised porosity and containing silicon Download PDFInfo
- Publication number
- EP2197794B1 EP2197794B1 EP08846541A EP08846541A EP2197794B1 EP 2197794 B1 EP2197794 B1 EP 2197794B1 EP 08846541 A EP08846541 A EP 08846541A EP 08846541 A EP08846541 A EP 08846541A EP 2197794 B1 EP2197794 B1 EP 2197794B1
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- EP
- European Patent Office
- Prior art keywords
- zeolite
- precursor
- surfactant
- particles
- ranging
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 147
- 239000010703 silicon Substances 0.000 title description 5
- 229910052710 silicon Inorganic materials 0.000 title description 5
- 239000010457 zeolite Substances 0.000 claims abstract description 89
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 79
- 239000002243 precursor Substances 0.000 claims abstract description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000011159 matrix material Substances 0.000 claims abstract description 39
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012798 spherical particle Substances 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000002459 porosimetry Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000443 aerosol Substances 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 65
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 23
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- 238000004448 titration Methods 0.000 claims description 8
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- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004411 aluminium Substances 0.000 claims 4
- 238000002360 preparation method Methods 0.000 abstract description 26
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- 239000000377 silicon dioxide Substances 0.000 abstract description 9
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 14
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- 150000001875 compounds Chemical class 0.000 description 8
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 8
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- 238000001179 sorption measurement Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 4
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- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002152 aqueous-organic solution Substances 0.000 description 3
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- 150000001768 cations Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- 239000002563 ionic surfactant Substances 0.000 description 3
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- 230000007935 neutral effect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
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- 239000012074 organic phase Substances 0.000 description 2
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
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- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J21/12—Silica and alumina
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/643—Pore diameter less than 2 nm
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/695—Pore distribution polymodal
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
Definitions
- the present invention relates to the field of materials comprising silicon, in particular metallosilicate materials and more specifically aluminosilicate materials, having a hierarchical porosity in the field of microporosity, mesoporosity and macroporosity. It also relates to the preparation of these materials which are obtained by the use of the so-called "aerosol" synthesis technique.
- a technique frequently used to generate materials having this bi-porosity is to create directly within zeolite crystals mesopores by subjecting the latter a hydrothermal treatment under water vapor also called "steaming". Under the effect of this treatment, the mobility of the tetrahedral atoms that make up the framework of the zeolite is increased to the point that some of these atoms are extracted from the network, which causes the formation of amorphous zone, which can be released to leave the room for mesoporous cavities ( AH Jansen, AJ Koster, KP De Jong, J. Phys. Chem. B, 2002, 106, 11905 ). The formation of such cavities can also be obtained by acid treatment of the zeolite ( H.
- the mesostructured materials are conventionally obtained via so-called soft chemistry synthesis methods which consist of bringing into contact in aqueous solution or in polar solvents inorganic precursors with structuring agents, generally molecular or macromolecular, ionic surfactants. or neutral.
- structuring agents generally molecular or macromolecular, ionic surfactants. or neutral.
- the control of electrostatic or hydrogen bonding interactions between the inorganic precursors and the structuring agent together with hydrolysis / condensation reactions of the inorganic precursor leads to a cooperative assembly of the organic and inorganic phases generating micellar aggregates of uniformly sized surfactants. and controlled within an inorganic matrix.
- the release of the porosity is then obtained by removing the surfactant, which is conventionally carried out by chemical extraction processes or by heat treatment.
- a first synthesis technique consists of synthesizing in the first step a mesostructured aluminosilicate material according to the conventional methods explained above and then, in the second step, impregnating this material with a structuring agent usually used in the synthesis of zeolite materials.
- a suitable hydrothermal treatment leads to a zeolitization of the amorphous walls (or walls) of the mesostructured aluminosilicate ( KR Koletstra, H. van Bekkum, JC Jansen, Chem. Commun., 1997, 2281 ; DT On, S. Kaliaguine, Angew.
- the idea used here is to simultaneously generate the development of an inorganic matrix with organized mesoporosity and the growth within this matrix of zeolite seeds so as to ideally obtain a mesostructured aluminosilicate material having walls (or walls).
- An alternative to these two techniques consists of a mixture of aluminum precursors and silicon in the presence of two structuring agents, one capable of generating a zeolite system, the other likely to generate mesostructuration.
- This solution is then subjected to two crystallization steps using variable hydrothermal treatment conditions, a first step which leads to the formation of the mesoporous structure with organized porosity and a second step which leads to the zeolitization of the walls (or walls ) amorphous ( A. Karlsson, M. Stöcker, R. Schmidt, Micropor. Mesopor. Mater., 1999, 27, 181 ; A. Karlsson, M. Stöcker, R. Schmidt, Stud. Surf. Sci.
- mesostructured / zeolite composite materials in order to benefit from the catalytic properties specific to each of these phases. This can be done by heat treatment of a mixture of a zeolite seed solution and a solution of mesostructured aluminosilicate seeds ( P. Prokesova, S. Mintova, J. Cejka, T. Bein, Micropor. Mesopor. Mater., 2003, 64, 165 ) or by growth of a zeolite layer on the surface of a pre-synthesized mesostructured aluminosilicate ( DT On, S. Kaliaguine, Angew. Chem. Int. Ed., 2002, 41, 1036 ).
- zeolite zeolite materials obtained by post-treatment of a zeolite we note that, from an experimental point of view, all these materials are obtained by direct precipitation of inorganic precursors in the presence or absence of structuring agents within an aqueous solution or in polar solvents, this step being mostly followed by one or more autoclave ripening steps.
- the elementary particles usually obtained do not have a regular shape and are generally characterized by a size ranging from 200 to 500 nm.
- one of the most common synthetic methods consists of using polystyrene beads as a macroporosity generating element and creating around these beads a zeolite network ( GS Zhu, Qiu SL, Gao FF, Li DS, YF Li, Wang RW, Gao B., Li BS, YH Guo, Xu RR, Z. Liu, O. Terasaki, J. Mater. Chem., 2001, 11, 6, 1687 ).
- the document EP1627853 discloses a hierarchical porosity material consisting of at least two elementary spherical particles, each of said spherical particles comprising zeolitic nanocrystals having a pore size of between 0.2 and 2 nm and a mesostructured silicon oxide matrix, having a pore size between 1.5 and 30 nm and having amorphous walls of thickness between 1 and 20 nm, said elementary spherical particles having a maximum diameter of 10 microns.
- the invention relates to a material with a hierarchical porosity consisting of at least two elementary spherical particles having a maximum diameter of 200 microns, at least one of said spherical particles comprising at least one matrix based on silicon oxide, said material exhibiting a macroporous volume measured by mercury porosimetry of between 0.05 and 1 ml / g, a mesoporous volume measured by nitrogen volumetry of between 0.01 and 1 ml / g and a microporous volume measured by nitrogen volumetry. between 0.03 and 0.4 ml / g, said matrix having crystallized walls, which consist of zeolite entities at the origin of the microporosity of the material.
- Said matrix based on silicon oxide optionally further comprises at least one element X selected from aluminum, iron, boron, indium and gallium, preferably aluminum.
- the present invention also relates to the preparation of the material according to the invention.
- the method for preparing the material according to the invention comprises a) the preparation of a clear solution containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one element X selected from aluminum, iron, boron, indium and gallium; b) mixing in solution at least one surfactant and at least said clear solution obtained according to a); c) the aerosol atomization of said solution obtained at
- step b) to lead to the formation of spherical droplets; d) drying said droplets; e) autoclaving the particles obtained according to d); f) drying said particles obtained according to e) and g) the removal of said structuring agent and said surfactant to obtain a crystallized material with hierarchical porosity in the range of microporosity, mesoporosity and macroporosity.
- microporosity induced by the crystallized walls of zeolite nature of the material according to the invention is consecutive not only to the use of a solution containing the precursor elements of zeolitic entities according to step a) of the process according to the invention, but also to the implementation of an autoclaving of the particles in accordance with step e) of the process for preparing the material according to the invention.
- the mesoporosity and the macroporosity of the material according to the invention are consecutive to the phenomenon of phase separation by spinodal decomposition of the organic phase generated by the presence of the surfactant and the inorganic phase resulting from the solution containing the precursor elements of zeolitic entities, this phase separation phenomenon being induced by the so-called aerosol technique according to step c) of the process according to the invention.
- the material according to the invention which comprises a mesoporous and macroporous inorganic matrix, based on silicon oxide, with microporous and crystallized walls, simultaneously exhibits the structural, textural and acid-base properties of the materials of the zeolite family and the textural properties of mesoporous materials and macroporous materials.
- the presence within the same spherical particle of micrometric or even nanometric size of mesopores and macropores in a microporous and crystallized inorganic matrix leads to a privileged access of the reagents and products of the reaction to the microporous sites during the use of the material.
- according to the invention as an adsorbent or as an acidic solid in potential industrial applications.
- the material according to the invention consists of spherical elementary particles, the diameter of these particles being at most equal to 200 ⁇ m, preferably less than 100 ⁇ m, advantageously varying from 50 nm to 20 ⁇ m, very advantageously to 50 nm. at 10 ⁇ m and even more advantageously from 50 to 300 nm.
- the limited size of these particles as well as their homogeneous spherical shape makes it possible to have a better diffusion of the reagents and the products of the reaction when the material according to the invention is used in potential industrial applications compared with materials. known from the state of the art in the form of elementary particles of non-homogeneous shape, that is to say irregular, and size often greater than 500 nm.
- the subject of the present invention is a material with a hierarchical porosity consisting of at least two elementary spherical particles having a maximum diameter of 200 microns, at least one of said spherical particles comprising at least one matrix based on silicon oxide and having crystallized walls, said material having a macroporous volume measured by mercury porosimetry of between 0.05 and 1 ml / g, a mesoporous volume measured by nitrogen volumetry of between 0.01 and 1 ml / g and a microporous volume measured by nitrogen volumetry between 0.03 and 0.4 ml / g.
- the term "hierarchically porous material” means a material having at least one, and generally several, spherical particles (s) having a triple porosity: a macroporosity characterized by a macroporous mercury volume included in a range ranging from 0.05 to 1 ml / g and preferably in a range of from 0.1 to 0.3 ml / g, a mesoporosity characterized by a mesoporous volume measured by nitrogen volumetry in a range of from 0 to , 01 to 1 ml / g and preferably in a range varying from 0.1 to 0.6 ml / g and a zeolite type microporosity whose characteristics (zeolite structural type, chemical composition of the zeolite framework) are function zeolite entities constituting the crystallized walls of each of the matrices spherical particles of the material according to the invention.
- a macroporosity characterized by a macropor
- the macroporosity is also characterized by the presence of macroporous domains ranging from 50 to 1000 nm and preferably in a range varying from 80 to 500 nm and / or resulting from an intraparticular textural macroporosity
- the mesoporosity is also characterized by the presence of mesoporous domains in a range of 2 to 50 nm and preferably in a range of 10 to 50 nm.
- the material according to the invention may also advantageously have elementary spherical particles without mesoporosity.
- a porosity of microporous nature may also result from the interlaying of the surfactant, used during the preparation of the material according to the invention, with the inorganic wall at the level of the organic-inorganic interface developed during the treatment. production of said material according to the invention.
- the matrix based on silicon oxide each forming spherical particles of the material according to the invention has crystallized walls consisting of zeolite entities, which are at the origin of the microporosity present within each spherical particles of the material according to the invention. Any zeolite and in particular, but not exhaustively, those listed in "Atlas of zeolite framework types", 5th revised edition, 2001, C.
- Baerlocher, WM Meier, DH Olson can be used for the formation of the zeolite entities constituting the crystallized walls of the matrix of each of the particles of the material according to the invention as soon as the dissolution of the precursor elements of these entities, namely at least one structuring agent, at least a silicic precursor and optionally at least one precursor of at least one element X selected from aluminum, iron, boron, indium and gallium, preferably aluminum, lead to obtaining a solution clear.
- the zeolite entities constituting the crystallized walls of the matrix of each of the particles of the material according to the invention and at the origin of the microporosity thereof preferably comprise at least one zeolite chosen from zeolites ZSM-5, ZSM-48 , ZSM-22, ZSM-23, ZBM-30, EU-2, EU-11, Silicalite, Beta, Zeolite A, Faujasite, Y, USY, VUSY, SDUSY, Mordenite, NU-87, NU-88, NU- 86, NU-85, IM-5, IM-12, Ferrierite and EU-1.
- the zeolite entities constituting the crystallized walls of the matrix of each of the particles of the material according to the invention comprise at least one zeolite chosen from zeolites of structural type MFI, BEA, FAU and LTA.
- the matrix based on silicon oxide forming each of the elementary spherical particles of the material according to the invention is either entirely silicic or it comprises, in addition to silicon, at least one element X chosen from aluminum iron, boron, indium and gallium, preferably aluminum.
- the zeolite entities constituting the crystallized walls of the matrix of each of the spherical particles of the material according to the invention and at the origin of the microporosity thereof advantageously comprise at least one zeolite either entirely silicic or containing, besides silicon at least one element X selected from aluminum, iron, boron, indium and gallium, preferably aluminum.
- the matrix of the material is in this case an aluminosilicate.
- This aluminosilicate has a Si / Al molar ratio equal to that of the solution of the silicic and aluminic precursors leading to the formation of the zeolite entities constituting the crystallized walls of the matrix.
- said elementary spherical particles constituting the material according to the invention have a maximum diameter equal to 200 microns, preferably less than 100 microns, advantageously between 50 nm and 20 ⁇ m, very advantageously between 50 nm and 10 nm. ⁇ m, and even more advantageously between 50 and 300 nm. More specifically, they are present in the material according to the invention in the form of aggregates.
- the material according to the invention advantageously has a specific surface area of between 100 and 1100 m 2 / g and very advantageously between 200 and 800 m 2 / g.
- the present invention also relates to the preparation of the material according to the invention.
- Said method for preparing the material according to the invention comprises: a) the preparation of a clear solution containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one element X selected from aluminum, iron, boron, indium and gallium, preferably aluminum; b) mixing in solution at least one surfactant and at least said clear solution obtained according to a); c) aerosol atomizing said solution obtained in step b) to lead to the formation of spherical droplets; d) drying said droplets; e) autoclaving the particles obtained according to d); f) drying said particles obtained according to e) and g) the removal of said structuring agent and said surfactant to obtain a crystallized material with hierarchical porosity in the range of microporosity, mesoporosity and macroporosity.
- the clear solution containing the precursor elements of zeolitic entities namely at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one less an X element selected from aluminum, iron, boron, indium and gallium, preferably aluminum, is made from operating protocols known to those skilled in the art.
- the silicic precursor used for the implementation of step a) of the process according to the invention is chosen from the precursors of silicon oxide well known to those skilled in the art.
- a silicic precursor chosen from the silica precursors usually used in the synthesis of zeolites for example uses solid silica powder, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane also called tetraethylorthosilicate (TEOS).
- TEOS tetraethylorthosilicate
- the silicic precursor is TEOS.
- the precursor of the element X can be any compound comprising the element X and which can release this element in solution, in particular in aqueous solution or aquo-organic, in reactive form.
- the aluminum precursor is advantageously an inorganic aluminum salt of formula AlZ 3 , Z being a halogen, a nitrate or a hydroxide.
- Z is chlorine.
- the aluminum precursor may also be an aluminum sulphate of formula Al 2 (SO 4 ) 3 .
- R is s-butyl.
- the aluminum precursor may also be sodium aluminate or alumina proper in one of its crystalline phases known to those skilled in the art (alpha, delta, teta, gamma), preferably in hydrated form or which can be hydrated.
- aluminic and silicic precursors may optionally be added in the form of a single compound comprising both aluminum atoms and silicon atoms, for example an amorphous alumina silica.
- the structuring agent used for carrying out step a) of the process according to the invention may be ionic or neutral depending on the zeolite to be synthesized. It is common to use the structuring agents of the following non-exhaustive list: nitrogenous organic cations such as tetrapropylammonium (TPA), elements of the family of alkalis (Cs, K, Na, etc.), ethercouronnes, diamines and any other structuring agent well known to those skilled in the art for the synthesis of zeolite.
- TPA tetrapropylammonium
- Cs, K, Na, etc. ethercouronnes
- diamines diamines and any other structuring agent well known to those skilled in the art for the synthesis of zeolite.
- the clear solution containing the zeolite entity precursor elements according to step a) of the process for preparing the material according to the invention is generally obtained by preparing a reaction mixture containing at least one silicic precursor, optionally at least one precursor of at least one precursor. at least one element X selected from aluminum, iron, boron, indium and gallium, preferably at least one aluminum precursor, and at least one structuring agent.
- the reaction mixture is either aqueous or aquo-organic, by example a water-alcohol mixture. It is preferred to work in a basic reaction medium during the various steps of the process according to the invention in order to promote the development of the zeolite entities constituting the crystallized walls of the matrix of each of the particles of the material according to the invention.
- the basicity of the solution is advantageously ensured by the basicity of the structuring agent used or by basification of the reaction mixture by the addition of a basic compound, for example an alkali metal hydroxide, preferably sodium hydroxide. .
- the reaction mixture may be placed under hydrothermal conditions under autogenous pressure, optionally by adding a gas, for example nitrogen, at a temperature between room temperature and 200 ° C., preferably between ambient temperature and 170 ° C. and still more preferably at a temperature which does not exceed 120 ° C. until the formation of a clear solution containing the precursor elements of the zeolite entities constituting the crystallized walls of the matrix of each of the spherical particles of the material according to the invention .
- a gas for example nitrogen
- the reaction mixture containing at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one element X selected from aluminum, iron, boron, indium and the gallium is cured at ambient temperature so as to obtain a clear solution containing the precursor elements of zeolite seeds capable of generating the formation of crystallized zeolite entities during the step e) of autoclaving the process for preparing the material according to the invention.
- the precursor elements of the zeolitic entities present in the clear solution are synthesized according to operating protocols known to those skilled in the art.
- a clear solution containing precursor elements of zeolite beta entities is produced from the operating protocol described by P. Prokesova, S. Mintova, J. Cejka, T. Bein et al., Micropor. Mesopor. Mater., 2003, 64, 165 .
- a clear solution containing precursor elements of zeolite Y entities is produced from the operating protocol described by Y. Liu, WZ Zhang, TJ Pinnavaia et al., J. Am. Chem. Soc., 2000, 122, 8791 .
- a clear solution containing precursor elements of zeolite faujasite entities is produced from the operating protocol described by KR Kloetstra, HW Zandbergen, Jansen CJ, H. vanBekkum, Microporous Mater., 1996, 6, 287 .
- a clear solution containing precursor elements of ZSM-5 zeolite species is carried out from the operating protocol described by AE Persson, BJ Schoeman, J. Sterte, J.-E. Otterstedt, Zeolifes, 1995, 15, 611 , the exact operating protocol which is the subject of example 1 of the present application.
- the clear solution containing the precursor elements of zeolite silicalite species constituting the walls of the material according to the invention is advantageously made from the operating protocol described by AE Persson, BJ Schoeman, J. Sterte, J.-E. Otterstedt, Zeolites, 1994, 14, 557 .
- the surfactant used is an ionic or nonionic surfactant or a mixture of both.
- the ionic surfactant is chosen from anionic surfactants such as sulphates, for example sodium dodecyl sulphate (SDS).
- the nonionic surfactant may be any copolymer having at least two parts of different polarities conferring properties of amphiphilic macromolecules.
- fluorinated copolymers - [CH 2 -CH 2 -CH 2 -CH 2
- a block copolymer consisting of poly (alkylene oxide) chains is preferably used.
- Said block copolymer is preferably a block copolymer having two, three or four blocks, each block consisting of a poly (alkylene oxide) chain.
- one of the blocks consists of a poly (alkylene oxide) chain of hydrophilic nature and the other block consists of a poly (alkylene oxide) chain of a nature hydrophobic.
- two of the blocks consist of a chain of poly (alkylene oxide) of hydrophilic nature while the other block, located between the two blocks with the hydrophilic parts, consists of a chain of poly (alkylene oxide) hydrophobic nature.
- the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains denoted (PEO) x and (PEO) z and the Poly (alkylene oxide) chains of hydrophobic nature are chains of poly (propylene oxide) denoted (PPO) y, poly (butylene oxide) chains, or mixed chains, each chain of which is a mixture of several alkylene oxide monomers.
- a compound is used. consisting of two chains of poly (ethylene oxide) and a poly (propylene oxide) chain and more particularly, it is the compound of formula (PEO) x - (PPO) y - (PEO) z where x is between 5 and 300 and y is between 33 and 300 and z is between 5 and 300.
- PEO poly (ethylene oxide)
- y poly (propylene oxide)
- PEO poly (propylene oxide) chain
- x is between 5 and 300 and y is between 33 and 300 and z is between 5 and 300.
- the values of x and z are the same.
- nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) are useful as nonionic surfactants in step b ) of the preparation process of the invention.
- Pluronic BASF
- Tetronic BASF
- Triton Sigma
- Tergitol Union Carbide
- Brij Brij
- two of the blocks consist of a poly (alkylene oxide) chain of hydrophilic nature and the other two blocks consist of a chain of poly (alkylene oxide) hydrophobic nature.
- the solution obtained at the end of step b) of the process for preparing the material according to the invention in which at least said surfactant and at least said clear solution obtained according to step a) are mixed can be acidic, neutral or basic.
- said solution is basic and preferably has a pH greater than 9, this pH value being generally imposed by the pH of the clear solution containing the precursor elements of zeolitic entities obtained according to step a) of the preparation process of the material according to the invention.
- the solution obtained at the end of step b) may be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent, in particular an alcohol, preferably ethanol.
- the amount of surfactant introduced into the mixture according to step b) of the preparation process according to the invention is defined with respect to the amount of inorganic material introduced into said mixture during the addition of the clear solution containing the precursor elements. of zeolitic entities obtained according to step a) of the process according to the invention.
- the amount of inorganic material corresponds to the amount of silicic precursor material and that of the element X precursor when present.
- the surfactant is such that the organic-inorganic binary system formed during the atomization step c) of the process for preparing the material according to the invention undergoes a phase separation characterized by the appearance of an interconnected biphasic network of which the mechanism of formation is a spinodal decomposition.
- the principle of phase separation via a mechanism of spinodal decomposition has been widely described by Nakanishi for obtaining silica gels in the presence of polymers ( K. Nakanishi, Journal of Porous Materials, 1997, 4, 67 ).
- the initial concentration of surfactant, introduced into the mixture, defined by c 0 is such that c 0 is less than or equal to c mc , the parameter c mc representing the micellar concentration criticism well known to those skilled in the art, that is to say the limit concentration beyond which occurs the phenomenon of self-arrangement of surfactant molecules in the solution.
- the concentration of surfactant molecules in the solution defined by step b) of the process for preparing the material according to the invention therefore does not lead to the formation of particular micellar phases.
- the concentration c 0 is less than the c mc
- the ratio n Inorganic / n Tensloactif is such that the composition of the binary system verifies the composition conditions for which a separation mechanism of phase occurs by spinodal decomposition and said solution referred to in step b) of the preparation process according to the invention is a basic water-alcohol mixture.
- the step of atomizing the mixture according to step c) of the preparation process according to the invention produces spherical droplets.
- the size distribution of these droplets is lognormal.
- the aerosol generator used here is a commercial model 9306A device provided by TSI having a 6-jet atomizer.
- the atomization of the solution is done in a chamber into which a carrier gas, a mixture O 2 / N 2 (dry air), is sent under a pressure P equal to 1.5 bar.
- step d) of the preparation process according to the invention said droplets are dried.
- This drying is carried out by transporting said droplets via the carrier gas, the O 2 / N 2 mixture, in PVC tubes, which leads to the gradual evaporation of the solution, for example from the basic aqueous-organic solution obtained.
- step b) of the process for preparing the material according to the invention and thus obtaining spherical elementary particles.
- This drying is perfect by a passage of said particles in an oven whose temperature can be adjusted, the usual range of temperature ranging from 50 to 600 ° C and preferably from 80 to 400 ° C, the residence time of these particles in the oven being of the order of the second.
- the particles are then harvested in a filter.
- the dried particles obtained according to step d) of the process according to the invention are autoclaved in the presence of a solvent.
- This step consists in placing said particles in a closed chamber in the presence of a solvent at a given temperature so as to work with autogenous pressure inherent to the operating conditions chosen.
- the solvent used is a protic polar solvent.
- the solvent used is water.
- the volume of solvent introduced is defined relative to the volume of the autoclave selected.
- the volume of solvent introduced is in a range of 0.01 to 20% relative to the volume of the autoclave chosen, preferably in a range of 0.05 to 5% and preferably in a range of 0, 05 to 1%.
- the autoclaving temperature is between 50 and 200 ° C, preferably between 60 and 170 ° C and more preferably between 60 and 120 ° C so as to allow the growth of zeolite entities in the walls of the matrix of each of the particles of the material according to the invention without generating large size zeolite crystals which would disorganize the mesoporosity and macroporosity created within each particle of the material according to the invention.
- Autoclaving is maintained over a period of 1 to 96 hours and preferably over a period of 20 to 50 hours.
- step f) of the preparation process according to the invention the drying of the particles after autoclaving is advantageously carried out by placing in an oven at a temperature of between 50 and 150 ° C.
- the element X is the aluminum element and where the sodium element is present in the clear solution obtained in accordance with step a) of the process according to the invention via the use of sodium hydroxide and / or a sodic structuring agent ensuring the basicity of said clear solution, it is preferred to carry out an additional ion exchange step allowing the exchange of the Na + cation by the NH 4 + cation between steps f) and g) of the process according to the invention.
- step g) This exchange, which leads to the formation of protons H + after step g) of the process according to the invention in the preferred case where the removal of the structuring agent and the surfactant is carried out by calcination under air, is carried out according to operating protocols well known to those skilled in the art.
- One of the usual methods consists in suspending the dried solid particles from step f) of the process according to the invention in an aqueous solution of ammonium nitrate. The whole is then refluxed for 1 to 6 hours. The particles are then recovered by filtration (centrifugation at 9000 rpm), washed and then dried by passing in an oven at a temperature between 50 and 150 ° C.
- This ion exchange / washing / drying cycle can be repeated several times and preferably two more times.
- This exchange cycle can also be performed after steps f) and g) of the process according to the invention. Under these conditions, step g) is then reproduced after the last exchange cycle so as to generate H + protons as explained above
- step g) of the preparation process according to the invention the elimination of the structuring agent and the surfactant, in order to obtain the material according to the invention with hierarchical porosity, is advantageously carried out by processes of chemical extraction or by heat treatment and preferably by calcination in air in a temperature range of 300 to 1000 ° C and more precisely in a range of 400 to 600 ° C for a period of 1 to 24 hours and preferably during a duration of 2 to 12 hours.
- the solution referred to in step b) of the preparation process according to the invention is a water-organic solvent mixture, preferably a basic one
- the surfactant concentration is less than the critical micellar concentration and that the n- inorganic ratio of the surfactant is such that the variation of the free mixture enthalpy ⁇ G m and the second derivative of the free enthalpy ⁇ 2 G / ⁇ 2 x are greater than 0 so that the evaporation of said aqueous-organic solution, preferably basic, during step c) of the preparation process according to the invention by the aerosol technique induces a separation phenomenon organic and inorganic phases by spinodal decomposition leading to the generation of the mesoporous and macroporous phases of the spherical particles of the material according to the invention.
- phase separation observed is consecutive to a progressive concentration, within each droplet, of the silicic precursor, optionally of the precursor of the element X, preferably of the aluminum precursor and of the surfactant resulting from evaporation of the aqueous-organic solution preferentially basic, until a concentration of reagents sufficient to cause said phenomenon.
- the hierarchically porous material of the present invention can be obtained in the form of powder, beads, pellets, granules, or extrusions, the shaping operations being carried out by conventional techniques known to those skilled in the art.
- the material having a hierarchical porosity according to the invention is obtained in the form of a powder, which consists of elementary spherical particles having a maximum diameter of 200 microns, which facilitates the possible diffusion of the reagents in the case of the use of the material according to the invention in a potential industrial application.
- the material of the invention with hierarchical porosity is characterized by several analysis techniques and in particular by large-angle X-ray diffraction (XRD), by nitrogen volumetry (BET), by mercury porosimetry, by electron microscopy. transmission (TEM), scanning electron microscopy (SEM) and X-ray fluorescence (FX).
- XRD large-angle X-ray diffraction
- BET nitrogen volumetry
- TEM transmission
- SEM scanning electron microscopy
- FX X-ray fluorescence
- the technique of X-ray diffraction at large angles makes it possible to characterize a crystallized solid defined by the repetition of a unitary unit or unit cell at the molecular scale.
- the X-ray analysis is performed on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength 1.5406 A).
- This indexing then allows the determination of the mesh parameters (abc) of the direct network.
- the wide-angle XRD analysis is therefore adapted to the structural characterization of the zeolite entities constituting the crystallized wall of the matrix of each of the elementary spherical particles constituting the material according to the invention.
- TEOS silicic precursor
- Al (O s C 4 H 9 ) 3 as an aluminum precursor
- TPAOH a structuring agent
- poly (ethylene oxide) 106 -poly (propylene oxide) 70 -poly (ethylene oxide) 106 (PEO 106 -PPO 70 -PEO 106 or F127) as surfactant exhibits the diffractogram associated with the Pnma symmetry group (No. 62) of zeolite ZSM-5 at large angles.
- Nitrogen volumetry which corresponds to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase in pressure at constant temperature, provides information on textural characteristics (pore diameter, porosity type, specific surface area). of the material obtained according to the process of the invention. In particular, it provides access to the total value of the microporous and mesoporous volume of the material.
- the shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the presence of the microporosity linked to the zeolitic entities constituting the crystallized walls of the matrix of each of the spherical particles of the material according to the invention. and the nature of mesoporosity.
- MFI zeolite entities ZSM-5
- the mercury porosimetry analysis corresponds to the intrusion of a volume of mercury characteristic of the existence of mesopores and macropores in the material according to the invention according to the ASTM D4284-83 standard at a maximum pressure of 4000 bar, using a surface tension of 484 dyne / cm, and a contact angle of 140 ° (value chosen according to the recommendations of the book " Technique of the engineer, treated analysis and characterization ", page 1050, written by J. Charpin and B. Rasneur ) and the pores are assumed to be cylindrical in shape. This technique is perfectly suited to the analysis of mesoporous and macroporous samples in addition to the nitrogen volumetric analysis technique described above.
- this technique makes it possible to access the value of the mesoporous mercury volume (V Hgmeso in ml / g) defined as being the mercury volume adsorbed by all the pores having a diameter included in the range of mesopores, namely between 3.6 nm and 50 nm (value of the upper limit as defined by the IUPAC standard).
- the macroporous mercury volume (V Hgmacro in ml / g) is defined as the mercury volume adsorbed by all the pores having a diameter greater than 50 nm.
- the mercury porosimetry analysis of a mesoporous and macroporous porosity material the microporous walls of the matrix of each of the spherical particles consist of zeolite entities ZSM-5 (MFI), obtained according to the method.
- MFI zeolite entities
- TEOS a silicic precursor
- Al (O s C 4 H 9 ) 3 as an aluminum precursor
- TPAOH as a structuring agent
- poly (ethylene oxide) 106 -poly (oxide of propylene) 70- poly (ethylene oxide) 106 (PEO 160 -PPO 70 -PEO 106 or F127) as surfactant leads to a mesoporous mercury volume ranging from 0.01 to 1 ml / g and a volume of macroporous mercury in a range of 0.05 to 1 ml / g.
- Transmission electron microscopy (TEM) analysis is a technique also widely used to characterize the mesoporosity and macroporosity of the material according to the invention. This allows the formation of an image of the studied solid, the observed contrasts being characteristic of the structural organization, the texture, the morphology or the chemical composition of the particles observed, the resolution of the technique reaching the maximum 0.2 nm.
- the TEM photos will be made from microtome sections of the sample in order to visualize a section of an elementary spherical particle of the material according to the invention.
- the morphology and size distribution of the elementary particles were established by scanning electron microscopy (SEM) photo analysis.
- the present invention also relates to the use of the hierarchically porous material according to the invention as an adsorbent for the control of pollution or as a molecular sieve for separation.
- the present invention therefore also relates to an adsorbent comprising the hierarchically porous material according to the invention. It is also advantageously used as an acid solid to catalyze reactions, for example those involved in the fields of refining and petrochemistry.
- this material When the hierarchically porous material according to the invention is used as a catalyst, this material may be associated with an inorganic matrix which may be inert or catalytically active and with a metallic phase.
- the inorganic matrix may be present simply as a binder to hold together the particles of said material in the various known forms of the catalysts (extrudates, pellets, beads, powders) or may be added as a diluent to impose the degree of conversion in a process which otherwise would progress at too fast a rate, leading to clogging of the catalyst as a result of a significant formation of coke.
- Typical inorganic matrices are, in particular, support materials for catalysts, such as the various forms of silica, alumina, silica-alumina, magnesia, zirconia, titanium oxides, boron oxides, aluminum phosphates, titanium, zirconium, clays such as kaolin, bentonite, montmorillonite, sepiolite, attapulgite, fuller's earth, synthetic porous materials such as SiO 2 -Al 2 O 3 , SiO 2 -ZrO 2 , SiO 2 -ThO 2 , SiO 2 -BeO SiO 2 -TiO 2 or any combination of these compounds.
- catalysts such as the various forms of silica, alumina, silica-alumina, magnesia, zirconia, titanium oxides, boron oxides, aluminum phosphates, titanium, zirconium, clays such as kaolin, bentonite, montmorillonite, sepio
- the inorganic matrix may be a mixture of different compounds, in particular an inert phase and an active phase.
- Said material of the present invention may also be associated with at least one zeolite and play the role of main active phase or additive.
- the metal phase can be introduced integrally on said material of the invention.
- cations or oxides chosen from the following elements: Cu, Ag, Ga, Mg, Ca , Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and all other element of the periodic table of elements.
- the catalyst compositions comprising the material of the present invention are generally suitable for carrying out the main hydrocarbon conversion processes and organic compound synthesis reactions.
- the catalyst compositions comprising the material of the invention advantageously find their application in isomerization, transalkylation and disproportionation, alkylation and dealkylation, hydration and dehydration, oligomerization and polymerization, cyclization reactions. , aromatization, cracking, reforming, hydrogenation and dehydrogenation, oxidation, halogenation, hydrocracking, hydroconversion, hydrotreatment, hydrodesulfurization and hydrodenitrogenation, catalytic removal nitrogen oxides, said reactions involving fillers comprising saturated and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated organic compounds and organic compounds containing nitrogen and / or sulfur as well as organic compounds containing other functional groups.
- the ratio V inorganic / V organic of the mixture resulting from step b) is calculated.
- TPAOH tetrapropylammonium hydroxide 20% by weight in an aqueous solution
- TPAOH tetrapropylammonium hydroxide
- demineralized water 9.2 mg of sodium hydroxide NaOH.
- 0.14 g of aluminum sec-butoxide (Al (O s C 4 H 9 ) 3 are then introduced, the hydrolysis of the aluminum precursor is carried out for 1 hour, 6 g of tetraethylorthosilicate (TEOS) are then added.
- TEOS tetraethylorthosilicate
- the harvested powder is then introduced into an oven set at a temperature of 250 ° C to complete their drying for a period of about one second.
- the harvested powder is then dried for 12 hours in an oven at 95 ° C.
- 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C. and pressures of the order of 5 bars) in the presence of 100 ⁇ l of demineralised water .
- the autoclave is provided with a system of "basket” or "cell” allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor.
- the autoclave is then heated to a temperature of 95 ° C for 48 hours. hours.
- the recovered powder is then dried in an oven at 95 ° C. for 12 hours.
- the solid is characterized by XRD, nitrogen volumetry, mercury porosimetry, TEM, SEM, FX.
- the TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the set being characteristic of an organic-inorganic phase separation obtained by a spinodal decomposition mechanism present before the calcination step.
- the macroporous mercury volume defined by mercury porosimetry is 0.5 ml / g (the value of the mercury mercury volume also obtained by mercury porosimetry is in perfect agreement with the value obtained by nitrogen volumetry).
- the wide-angle XRD analysis leads to obtaining the diffractogram characteristic of the zeolite ZSM-5 (size of the micopores, measured by XRD, of the order of 0.55 nm).
- the molar Si / Al ratio obtained by FX is 50.
- An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
- Example 2 Preparation of a mesoporous and macroporous porosity material whose microporous walls consist of crystallized entities of zeolite silicalite (MFI).
- MFI zeolite silicalite
- the whole is left stirring for 10 minutes.
- the droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O 2 / N 2 mixture in PVC tubes. They are then introduced into an oven set at a drying temperature set at 250 ° C. The harvested powder is then dried for 12 hours in an oven at 95 ° C. 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C.
- the autoclave is provided with a system of "basket” or “cell” allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor.
- the autoclave is then heated to a temperature of 95 ° C for 36 hours.
- the recovered powder is then dried in an oven at 95 ° C. for 12 hours.
- the powder is then calcined under air for 5 hours at 550 ° C.
- the solid is characterized by XRD, nitrogen volumetry, mercury porosimetry, TEM, SEM.
- the TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the set being characteristic of an organic-inorganic phase separation obtained by a spinodal decomposition mechanism present before the calcination step.
- the presence of zeolite entities in the walls of the material is also clearly visible during the study by electron diffraction of the michronotropic sections with a thickness of the order of 70 nm on localized areas of the order of 100 nm.
- Nitrogen volumetric analysis combined with analysis by the ⁇ s method leads to a microporous volume V micro value of 0.3 ml / g (N 2 ), a mesoporous V meso volume value of 0, 6 ml / g (N 2 ) and a specific surface area of the final material of S 680 m 2 / g.
- the macroporous mercury volume defined by mercury porosimetry is 0.5 ml / g (the value of the mesoporous mercury volume also obtained is in perfect agreement with the value obtained by volumetric nitrogen).
- the wide-angle XRD analysis leads to obtaining the diffractogram characteristic of the zeolite silicalite (size of the micropores, measured by XRD, of the order of 0.55 nm).
- An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
- tetraethylammonium hydroxide hydroxide 20% by weight in an aqueous solution
- TEAOH tetraethylammonium hydroxide hydroxide
- demineralized water 7.8 g of demineralized water and 0.03 g of sodium hydroxide NaOH.
- 0.14 g of aluminum sec-butoxide (Al (O s C 4 H 9 ) 3 ) are then introduced.
- the whole is left stirring for 10 minutes.
- the hydrolysis of the aluminum precursor is carried out for 1 hour. 6 g of tetraethylorthosilicate (TEOS) are then added.
- TEOS tetraethylorthosilicate
- the harvested powder is then dried for 12 hours in an oven at 95 ° C.
- 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C. and pressures of the order of 5 bars) in the presence of 150 ⁇ l of demineralised water .
- the autoclave is provided with a system of "basket” or “cell” allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor.
- the autoclave is then heated to a temperature of 95 ° C for 48 hours.
- the recovered powder is then dried in an oven at 95 ° C. for 12 hours.
- the powder is then calcined under air for 5 hours at 550 ° C.
- the solid is characterized by XRD, nitrogen volumetry, mercury porosimetry, TEM, SEM, FX.
- the TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the whole being characteristic of a phase separation organic - inorganic obtained by a spinodal decomposition mechanism present before the calcination step.
- the macroporous mercury volume defined by mercury porosimetry is 0.3 ml / g (the value of the mesoporous mercury volume also obtained is in perfect agreement with the value obtained by nitrogen volumetry).
- the wide-angle X-ray analysis leads to the characteristic diffractogram of zeolite beta (size of the micopores, measured by XRD, of the order of 0.66 nm).
- the molar Si / Al ratio obtained by FX is 50.
- An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
- the whole is left stirring for 10 minutes.
- the droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O 2 / N 2 mixture in PVC tubes. They are then introduced into an oven set at a temperature drying time set at 250 ° C. The harvested powder is then dried for 12 hours in an oven at 95 ° C. 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C.
- the autoclave is provided with a system of "basket” or “cell” allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor.
- the autoclave is then heated to a temperature of 95 ° C for 48 hours.
- the recovered powder is then dried in an oven at 95 ° C. for 12 hours.
- the powder is then calcined under air for 5 hours at 550 ° C.
- the solid is characterized by XRD and at large angles, by nitrogen volumetry, by mercury porosimetry, by TEM, by SEM and by ICP, by FX.
- the TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the set being characteristic of an organic-inorganic phase separation obtained by a spinodal decomposition mechanism present before the calcination step.
- the presence of zeolite entities in the walls of the material is also clearly visible during the study by electron diffraction of the michronotropic sections with a thickness of the order of 70 nm on localized areas of the order of 100 nm.
- the macroporous mercury volume defined by mercury porosimetry is 0.5 ml / g (the value of the mesoporous mercury volume also obtained is in perfect agreement with the value obtained by volumetric nitrogen).
- the wide-angle XRD analysis leads to obtaining the diffractogram characteristic of zeolite Y (size of the micopores, measured by XRD, of the order of 0.8 nm).
- the Si / Al molar ratio obtained by FX is 8.
- An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
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Abstract
Description
La présente invention se rapporte au domaine des matériaux comprenant du silicium, notamment des matériaux métallosilicates et plus précisément des matériaux aluminosilicates, présentant une porosité hiérarchisée dans le domaine de la microporosité, de la mésoporosité et de la macroporosité. Elle concerne également la préparation de ces matériaux qui sont obtenus par l'emploi de la technique de synthèse dite "aérosol".The present invention relates to the field of materials comprising silicon, in particular metallosilicate materials and more specifically aluminosilicate materials, having a hierarchical porosity in the field of microporosity, mesoporosity and macroporosity. It also relates to the preparation of these materials which are obtained by the use of the so-called "aerosol" synthesis technique.
Les nouvelles stratégies de synthèse permettant d'obtenir des matériaux à porosité bien définie dans une très large gamme, allant des matériaux microporeux aux matériaux macroporeux en passant par des matériaux à porosité hiérarchisée, c'est-à-dire ayant des pores de plusieurs tailles, connaissent un très large développement au sein de la communauté scientifique depuis le milieu des années 90 (
Une technique fréquemment employée pour générer des matériaux présentant cette bi-porosité consiste à créer directement au sein de cristaux de zéolithe des mésopores en faisant subir à cette dernière un traitement hydrothermal sous vapeur d'eau encore appelé "steaming". Sous l'effet de ce traitement, la mobilité des atomes tétraédriques qui composent la charpente de la zéolithe est accrue au point que certains de ces atomes sont extraits du réseau, ce qui engendre la formation de zone amorphe, qui peuvent être dégagés pour laisser la place à des cavités mésoporeuses (
Plus récemment, de nombreux travaux ont porté sur l'élaboration de matériaux mixtes mésostructuré/zéolithe, les matériaux mésostructurés présentant l'avantage supplémentaire d'avoir une porosité parfaitement organisée et calibrée dans la gamme des mésopores.More recently, many studies have focused on the development of mixed mesostructured / zeolite materials, the mesostructured materials having the additional advantage of having a perfectly organized and calibrated porosity in the range of mesopores.
Nous rappelons ici brièvement que les matériaux mésostructurés sont classiquement obtenus via des méthodes de synthèse dites de chimie douce qui consistent à mettre en présence en solution aqueuse ou dans des solvants polaires des précurseurs inorganiques avec des agents structurants, généralement des tensioactifs moléculaires ou macromoléculaires, ioniques ou neutres. Le contrôle des interactions électrostatiques ou par liaisons hydrogènes entre les précurseurs inorganiques et l'agent structurant conjointement lié à des réactions d'hydrolyse/condensation du précurseur inorganique conduit à un assemblage coopératif des phases organique et inorganique générant des agrégats micellaires de tensioactifs de taille uniforme et contrôlée au sein d'une matrice inorganique. La libération de la porosité est ensuite obtenue par élimination du tensioactif, celle-ci étant réalisée classiquement par des procédés d'extraction chimique ou par traitement thermique. En fonction de la nature des précurseurs inorganiques et de l'agent structurant employé ainsi que des conditions opératoires imposées, plusieurs familles de matériaux mésostructurés ont été développées comme la famille des M41S obtenue via l'emploi de sels d'ammonium quaternaire comme agent structurant (
Plusieurs techniques de synthèse permettant l'élaboration de ces matériaux mixtes mésostructuré/zéolithe ont ainsi été répertoriées dans la littérature ouverte. Une première technique de synthèse consiste à synthétiser en première étape un matériau aluminosilicate mésostructuré selon les méthodes classiques explicitées ci-dessus puis, en deuxième étape, à imprégner ce matériau avec un agent structurant habituellement utilisé dans la synthèse de matériaux zéolithiques. Un traitement hydrothermique adapté conduit à une zéolithisation des parois (ou murs) amorphes de l'aluminosilicate mésostructuré de départ (
Nous notons qu'il est également possible d'élaborer directement des matériaux composites mésostructuré/zéolithe de façon à bénéficier des propriétés catalytiques propres à chacune de ces phases. Ceci peut se faire par traitement thermique d'un mélange d'une solution de germes de zéolithes et d'une solution de germes d'aluminosilicates mésostructurés (
En excluant les matériaux zéolithiques mésoporeux obtenus par post-traitement d'une zéolithe, nous notons que, d'un point de vue expérimental, tous ces matériaux sont obtenus par précipitation directe de précurseurs inorganiques en présence ou non d'agents structurants au sein d'une solution aqueuse ou dans des solvants polaires, cette étape étant la plupart du temps suivie par une ou plusieurs étapes de mûrissement en autoclave. Les particules élémentaires habituellement obtenues ne présentent pas de forme régulière et sont caractérisées généralement par une taille variant de 200 à 500 nm.Excluding the zeolite zeolite materials obtained by post-treatment of a zeolite, we note that, from an experimental point of view, all these materials are obtained by direct precipitation of inorganic precursors in the presence or absence of structuring agents within an aqueous solution or in polar solvents, this step being mostly followed by one or more autoclave ripening steps. The elementary particles usually obtained do not have a regular shape and are generally characterized by a size ranging from 200 to 500 nm.
Plusieurs travaux ont également porté sur l'élaboration de matériaux présentant à la fois une micro et une macroporosité. A titre d'exemple, une des méthodes de synthèse les plus courantes consiste à utiliser des billes de polystyrène comme élément générateur de la macroporosité et à créer autour de ces billes un réseau zéolithique (
Le document
L'invention concerne un matériau à porosité hiérarchisée constitué d'au moins deux particules sphériques élémentaires ayant un diamètre maximal de 200 microns, l'une au moins desdites particules sphériques comprend au moins une matrice à base d'oxyde de silicium, ledit matériau présentant un volume macroporeux mesuré par porosimétrie au mercure compris entre 0,05 et 1 ml/g, un volume mésoporeux mesuré par volumétrie à l'azote compris entre 0,01 et 1 ml/g et un volume microporeux mesuré par volumétrie à l'azote compris entre 0,03 et 0,4 ml/g, ladite matrice présentant des parois cristallisées, lesquelles sont constituées d'entités zéolithiques à l'origine de la microporosité du matériau. Ladite matrice à base d'oxyde de silicium comprend éventuellement, en outre, au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium, de préférence l'aluminium. La présente invention concerne également la préparation du matériau selon l'invention. Le procédé de préparation du matériau selon l'invention comprend a) la préparation d'une solution limpide contenant les éléments précurseurs d'entités zéolithiques, à savoir au moins un agent structurant, au moins un précurseur silicique et éventuellement au moins un précurseur d'au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium ; b) le mélange en solution d'au moins un tensioactif et d'au moins ladite solution limpide obtenue selon a) ; c) l'atomisation par aérosol de ladite solution obtenue àThe invention relates to a material with a hierarchical porosity consisting of at least two elementary spherical particles having a maximum diameter of 200 microns, at least one of said spherical particles comprising at least one matrix based on silicon oxide, said material exhibiting a macroporous volume measured by mercury porosimetry of between 0.05 and 1 ml / g, a mesoporous volume measured by nitrogen volumetry of between 0.01 and 1 ml / g and a microporous volume measured by nitrogen volumetry. between 0.03 and 0.4 ml / g, said matrix having crystallized walls, which consist of zeolite entities at the origin of the microporosity of the material. Said matrix based on silicon oxide optionally further comprises at least one element X selected from aluminum, iron, boron, indium and gallium, preferably aluminum. The present invention also relates to the preparation of the material according to the invention. The method for preparing the material according to the invention comprises a) the preparation of a clear solution containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one element X selected from aluminum, iron, boron, indium and gallium; b) mixing in solution at least one surfactant and at least said clear solution obtained according to a); c) the aerosol atomization of said solution obtained at
l'étape b) pour conduire à la formation de gouttelettes sphériques ; d) le séchage desdites gouttelettes ; e) l'autoclavage des particules obtenues selon d) ; f) le séchage desdites particules obtenues selon e) et g) l'élimination dudit agent structurant et dudit tensioactif pour l'obtention d'un matériau cristallisé à porosité hiérarchisée dans la gamme de la microporosité, de la mésoporosité et de la macroporosité.step b) to lead to the formation of spherical droplets; d) drying said droplets; e) autoclaving the particles obtained according to d); f) drying said particles obtained according to e) and g) the removal of said structuring agent and said surfactant to obtain a crystallized material with hierarchical porosity in the range of microporosity, mesoporosity and macroporosity.
La microporosité induite par les parois cristallisées de nature zéolithique du matériau selon l'invention est consécutive non seulement à l'emploi d'une solution contenant les éléments précurseurs d'entités zéolithiques conformément à l'étape a) du procédé selon l'invention mais également à la mise en oeuvre d'un autoclavage des particules conformément à l'étape e) du procédé de préparation du matériau selon l'invention. La mésoporosité et la macroporosité du matériau selon l'invention sont consécutives au phénomène de séparation de phase par décomposition spinodale de la phase organique générée par la présence du tensioactif et de la phase inorganique issue de la solution contenant les éléments précurseurs d'entités zéolithiques, ce phénomène de séparation de phase étant induit par la technique dite aérosol conformément à l'étape c) du procédé selon l'invention.The microporosity induced by the crystallized walls of zeolite nature of the material according to the invention is consecutive not only to the use of a solution containing the precursor elements of zeolitic entities according to step a) of the process according to the invention, but also to the implementation of an autoclaving of the particles in accordance with step e) of the process for preparing the material according to the invention. The mesoporosity and the macroporosity of the material according to the invention are consecutive to the phenomenon of phase separation by spinodal decomposition of the organic phase generated by the presence of the surfactant and the inorganic phase resulting from the solution containing the precursor elements of zeolitic entities, this phase separation phenomenon being induced by the so-called aerosol technique according to step c) of the process according to the invention.
Le matériau selon l'invention qui comprend une matrice inorganique mésoporeuse et macroporeuse, à base d'oxyde de silicium, aux parois microporeuses et cristallisées présente simultanément les propriétés structurales, texturales et d'acido-basicité propres aux matériaux de la famille des zéolithes et les propriétés texturales propres aux matériaux mésoporeux et aux matériaux macroporeux. La présence au sein d'une même particule sphérique de taille micrométrique voire nanométrique de mésopores et de macropores dans une matrice inorganique microporeuse et cristallisée conduit à un accès privilégié des réactifs et des produits de la réaction aux sites microporeux lors de l'emploi du matériau selon l'invention en tant qu'adsorbant ou que solide acide dans des applications industrielles potentielles. De plus, le matériau selon l'invention est constitué de particules élémentaires sphériques, le diamètre de ces particules étant au maximum égal à 200 µm, de préférence inférieur à 100 µm, variant avantageusement de 50 nm à 20 µm, très avantageusement de 50 nm à 10 µm et de manière encore plus avantageuse de 50 à 300 nm. La taille limitée de ces particules ainsi que leur forme sphérique homogène permet d'avoir une meilleure diffusion des réactifs et des produits de la réaction lors de l'emploi du matériau selon l'invention dans des applications industrielles potentielles comparativement à des matériaux connus de l'état de la technique se présentant sous la forme de particules élémentaires de forme non homogène, c'est-à-dire irrégulière, et de taille souvent supérieure à 500 nm.The material according to the invention, which comprises a mesoporous and macroporous inorganic matrix, based on silicon oxide, with microporous and crystallized walls, simultaneously exhibits the structural, textural and acid-base properties of the materials of the zeolite family and the textural properties of mesoporous materials and macroporous materials. The presence within the same spherical particle of micrometric or even nanometric size of mesopores and macropores in a microporous and crystallized inorganic matrix leads to a privileged access of the reagents and products of the reaction to the microporous sites during the use of the material. according to the invention as an adsorbent or as an acidic solid in potential industrial applications. In addition, the material according to the invention consists of spherical elementary particles, the diameter of these particles being at most equal to 200 μm, preferably less than 100 μm, advantageously varying from 50 nm to 20 μm, very advantageously to 50 nm. at 10 μm and even more advantageously from 50 to 300 nm. The limited size of these particles as well as their homogeneous spherical shape makes it possible to have a better diffusion of the reagents and the products of the reaction when the material according to the invention is used in potential industrial applications compared with materials. known from the state of the art in the form of elementary particles of non-homogeneous shape, that is to say irregular, and size often greater than 500 nm.
La présente invention a pour objet un matériau à porosité hiérarchisée constitué d'au moins deux particules sphériques élémentaires ayant un diamètre maximal de 200 microns, l'une au moins desdites particules sphériques comprend au moins une matrice à base d'oxyde de silicium et présentant des parois cristallisées, ledit matériau présentant un volume macroporeux mesuré par porosimétrie au mercure compris entre 0,05 et 1 ml/g, un volume mésoporeux mesuré par volumétrie à l'azote compris entre 0,01 et 1 ml/g et un volume microporeux mesuré par volumétrie à l'azote compris entre 0,03 et 0,4 ml/g.The subject of the present invention is a material with a hierarchical porosity consisting of at least two elementary spherical particles having a maximum diameter of 200 microns, at least one of said spherical particles comprising at least one matrix based on silicon oxide and having crystallized walls, said material having a macroporous volume measured by mercury porosimetry of between 0.05 and 1 ml / g, a mesoporous volume measured by nitrogen volumetry of between 0.01 and 1 ml / g and a microporous volume measured by nitrogen volumetry between 0.03 and 0.4 ml / g.
Par matériau à porosité hiérarchisée, on entend au sens de la présente invention un matériau présentant au moins une, et généralement plusieurs, particule(s) sphérique(s) ayant une triple porosité : une macroporosité caractérisée par un volume mercure macroporeux compris dans une gamme variant de 0,05 à 1 ml/g et de préférence dans une gamme variant de 0,1 à 0,3 ml/g, une mésoporosité caractérisée par un volume mésoporeux mesuré par volumétrie à l'azote compris dans une gamme variant de 0,01 à 1 ml/g et de préférence dans une gamme variant de 0,1 à 0,6 ml/g et une microporosité de type zéolithique dont les caractéristiques (type structural de la zéolithe, composition chimique de la charpente zéolithique) sont fonction des entités zéolithiques constitutives des parois cristallisées de chacune des matrices des particules sphériques du matériau selon l'invention. La macroporosité est également caractérisée par la présence de domaines macroporeux compris dans une gamme variant de 50 à 1000 nm et de préférence dans une gamme variant de 80 à 500 nm et/ou résulte d'une macroporosité texturale intraparticulaire, la mésoporosité est aussi caractérisée par la présence de domaines mésoporeux compris dans une gamme variant de 2 à 50 nm et de préférence dans une gamme variant de 10 à 50 nm. Le matériau selon l'invention peut également avantageusement présenter des particules sphériques élémentaires dépourvues de mésoporosité. Il est à noter qu'une porosité de nature microporeuse peut également résulter de l'imbrication du tensioactif, utilisé lors de la préparation du matériau selon l'invention, avec la paroi inorganique au niveau de l'interface organique-inorganique développée lors de l'élaboration dudit matériau selon l'invention. Conformément à l'invention, la matrice à base d'oxyde de silicium formant chacune des particules sphériques du matériau selon l'invention présente des parois cristallisées constituées d'entités zéolithiques, lesquelles sont à l'origine de la microporosité présente au sein de chacune des particules sphériques du matériau selon l'invention. Toute zéolithe et en particulier, mais de façon non exhaustive, celles répertoriées dans
Conformément à l'invention, la matrice à base d'oxyde de silicium formant chacune des particules sphériques élémentaires du matériau selon l'invention est soit entièrement silicique soit, elle comprend, outre du silicium, au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium, de préférence l'aluminium. Ainsi, les entités zéolithiques constitutives des parois cristallisées de la matrice de chacune des particules sphériques du matériau selon l'invention et à l'origine de la microporosité de celui-ci comprennent avantageusement au moins une zéolithe soit entièrement silicique soit contenant, outre du silicium, au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium, de préférence l'aluminium. Lorsque X est l'aluminium, la matrice du matériau est dans ce cas un aluminosilicate. Cet aluminosilicate présente un rapport molaire Si/Al égal à celui de la solution des précurseurs silicique et aluminique conduisant à la formation des entités zéolithiques constitutives des parois cristallisées de la matrice. Conformément à l'invention, lesdites particules sphériques élémentaires constituant le matériau selon l'invention ont un diamètre maximal égal à 200 microns, de préférence inférieur à 100 microns, avantageusement compris entre 50 nm et 20 µm, très avantageusement compris entre 50 nm et 10 µm, et de manière encore plus avantageuse compris entre 50 et 300 nm. Plus précisément, elles sont présentes dans le matériau selon l'invention sous la forme d'agrégats.According to the invention, the matrix based on silicon oxide forming each of the elementary spherical particles of the material according to the invention is either entirely silicic or it comprises, in addition to silicon, at least one element X chosen from aluminum iron, boron, indium and gallium, preferably aluminum. Thus, the zeolite entities constituting the crystallized walls of the matrix of each of the spherical particles of the material according to the invention and at the origin of the microporosity thereof advantageously comprise at least one zeolite either entirely silicic or containing, besides silicon at least one element X selected from aluminum, iron, boron, indium and gallium, preferably aluminum. When X is aluminum, the matrix of the material is in this case an aluminosilicate. This aluminosilicate has a Si / Al molar ratio equal to that of the solution of the silicic and aluminic precursors leading to the formation of the zeolite entities constituting the crystallized walls of the matrix. According to the invention, said elementary spherical particles constituting the material according to the invention have a maximum diameter equal to 200 microns, preferably less than 100 microns, advantageously between 50 nm and 20 μm, very advantageously between 50 nm and 10 nm. μm, and even more advantageously between 50 and 300 nm. More specifically, they are present in the material according to the invention in the form of aggregates.
Le matériau selon l'invention présente avantageusement une surface spécifique comprise entre 100 et 1100 m2/g et de manière très avantageuse comprise entre 200 et 800 m2/g.The material according to the invention advantageously has a specific surface area of between 100 and 1100 m 2 / g and very advantageously between 200 and 800 m 2 / g.
La présente invention a également pour objet la préparation du matériau selon l'invention. Ledit procédé de préparation du matériau selon l'invention comprend : a) la préparation d'une solution limpide contenant les éléments précurseurs d'entités zéolithiques, à savoir au moins un agent structurant, au moins un précurseur silicique et éventuellement au moins un précurseur d'au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium, de préférence l'aluminium ; b) le mélange en solution d'au moins un tensioactif et d'au moins ladite solution limpide obtenue selon a) ; c) l'atomisation par aérosol de ladite solution obtenue à l'étape b) pour conduire à la formation de gouttelettes sphériques ; d) le séchage desdites gouttelettes ; e) l'autoclavage des particules obtenues selon d) ; f) le séchage desdites particules obtenues selon e) et g) l'élimination dudit agent structurant et dudit tensioactif pour l'obtention d'un matériau cristallisé à porosité hiérarchisée dans la gamme de la microporosité, de la mésoporosité et de la macroporosité.The present invention also relates to the preparation of the material according to the invention. Said method for preparing the material according to the invention comprises: a) the preparation of a clear solution containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one element X selected from aluminum, iron, boron, indium and gallium, preferably aluminum; b) mixing in solution at least one surfactant and at least said clear solution obtained according to a); c) aerosol atomizing said solution obtained in step b) to lead to the formation of spherical droplets; d) drying said droplets; e) autoclaving the particles obtained according to d); f) drying said particles obtained according to e) and g) the removal of said structuring agent and said surfactant to obtain a crystallized material with hierarchical porosity in the range of microporosity, mesoporosity and macroporosity.
Conformément à l'étape a) du procédé de préparation selon l'invention, la solution limpide contenant les éléments précurseurs d'entités zéolithiques, à savoir au moins un agent structurant, au moins un précurseur silicique et éventuellement au moins un précurseur d'au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium, de préférence l'aluminium, est réalisée à partir de protocoles opératoires connus de l'Homme du métier.According to step a) of the preparation process according to the invention, the clear solution containing the precursor elements of zeolitic entities, namely at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one less an X element selected from aluminum, iron, boron, indium and gallium, preferably aluminum, is made from operating protocols known to those skilled in the art.
Le précurseur silicique utilisé pour la mise en oeuvre de l'étape a) du procédé selon l'invention est choisi parmi les précurseurs d'oxyde de silicium bien connus de l'Homme du métier. En particulier, on utilise avantageusement un précurseur silicique choisi parmi les précurseurs de silice habituellement utilisés dans la synthèse des zéolithes, par exemple on utilise de la silice solide en poudre, de l'acide silicique, de la silice colloïdale, de la silice dissoute ou du tétraéthoxysilane encore appelé tétraéthylorthosilicate (TEOS). De manière préférée, le précurseur silicique est le TEOS.The silicic precursor used for the implementation of step a) of the process according to the invention is chosen from the precursors of silicon oxide well known to those skilled in the art. In particular, it is advantageous to use a silicic precursor chosen from the silica precursors usually used in the synthesis of zeolites, for example uses solid silica powder, silicic acid, colloidal silica, dissolved silica or tetraethoxysilane also called tetraethylorthosilicate (TEOS). Preferably, the silicic precursor is TEOS.
Le précurseur de l'élément X, éventuellement utilisé pour la mise en oeuvre de l'étape a) du procédé selon l'invention, peut être tout composé comprenant l'élément X et pouvant libérer cet élément en solution, notamment en solution aqueuse ou aquo-organique, sous forme réactive. Dans le cas préféré où X est l'aluminium, le précurseur aluminique est avantageusement un sel inorganique d'aluminium de formule AlZ3, Z étant un halogène, un nitrate ou un hydroxyde. De préférence, Z est le chlore. Le précurseur aluminique peut également être un sulfate d'aluminium de formule Al2(SO4)3. Le précurseur aluminique peut être aussi un précurseur organométallique de formule Al(OR)3 ou R = éthyle, isopropyle, n-butyle, s-butyle (Al(OsC4H9)3) ou t-butyle ou un précurseur chélaté tel que l'aluminium acétylacétonate (Al(C5H8O2)3). De préférence, R est le s-butyle. Le précurseur aluminique peut aussi être de l'aluminate de sodium ou de l'alumine proprement dite sous l'une de ses phases cristallines connues de l'Homme du métier (alpha, delta, teta, gamma), de préférence sous forme hydratée ou qui peut être hydratée.The precursor of the element X, optionally used for the implementation of step a) of the process according to the invention, can be any compound comprising the element X and which can release this element in solution, in particular in aqueous solution or aquo-organic, in reactive form. In the preferred case where X is aluminum, the aluminum precursor is advantageously an inorganic aluminum salt of formula AlZ 3 , Z being a halogen, a nitrate or a hydroxide. Preferably, Z is chlorine. The aluminum precursor may also be an aluminum sulphate of formula Al 2 (SO 4 ) 3 . The aluminic precursor can also be an organometallic precursor of formula Al (OR) 3 or R = ethyl, isopropyl, n-butyl, s-butyl (Al (O s C 4 H 9 ) 3 ) or t-butyl or a chelated precursor such as aluminum acetylacetonate (Al (C 5 H 8 O 2 ) 3 ). Preferably, R is s-butyl. The aluminum precursor may also be sodium aluminate or alumina proper in one of its crystalline phases known to those skilled in the art (alpha, delta, teta, gamma), preferably in hydrated form or which can be hydrated.
On peut également utiliser des mélanges des précurseurs cités ci-dessus. Certains ou l'ensemble des précurseurs aluminiques et siliciques peuvent éventuellement être ajoutés sous la forme d'un seul composé comprenant à la fois des atomes d'aluminium et des atomes de silicium, par exemple une silice alumine amorphe.It is also possible to use mixtures of the precursors mentioned above. Some or all of the aluminic and silicic precursors may optionally be added in the form of a single compound comprising both aluminum atoms and silicon atoms, for example an amorphous alumina silica.
L'agent structurant utilisé pour la mise en oeuvre de l'étape a) du procédé selon l'invention peut être ionique ou neutre selon la zéolithe à synthétiser. Il est fréquent d'utiliser les agents structurants de la liste non exhaustive suivante : des cations organiques azotés tel que le tétrapropylammonium (TPA), des éléments de la famille des alcalins (Cs, K, Na, etc.), des éthercouronnes, des diamines ainsi que tout autre agent structurant bien connu de l'Homme de l'Art pour la synthèse de zéolithe.The structuring agent used for carrying out step a) of the process according to the invention may be ionic or neutral depending on the zeolite to be synthesized. It is common to use the structuring agents of the following non-exhaustive list: nitrogenous organic cations such as tetrapropylammonium (TPA), elements of the family of alkalis (Cs, K, Na, etc.), ethercouronnes, diamines and any other structuring agent well known to those skilled in the art for the synthesis of zeolite.
On obtient généralement la solution limpide contenant les éléments précurseurs d'entités zéolithiques selon l'étape a) du procédé de préparation du matériau selon l'invention en préparant un mélange réactionnel renfermant au moins un précurseur silicique, éventuellement au moins un précurseur d'au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium, de préférence au moins un précurseur aluminique, et au moins un agent structurant. Le mélange réactionnel est soit aqueux soit aquo-organique, par exemple un mélange eau-alcool. Il est préféré de travailler dans un milieu réactionnel basique au cours des diverses étapes du procédé selon l'invention afin de favoriser le développement des entités zéolithiques constitutives des parois cristallisées de la matrice de chacune des particules du matériau selon l'invention. La basicité de la solution est avantageusement assurée par la basicité de l'agent structurant employé ou bien par basification du mélange réactionnel par l'ajout d'un composé basique, par exemple un hydroxyde de métal alcalin, de préférence de l'hydroxyde de sodium. Le mélange réactionnel peut être mis sous conditions hydrothermales sous une pression autogène, éventuellement en ajoutant un gaz, par exemple de l'azote, à une température comprise entre la température ambiante et 200°C, de préférence entre la température ambiante et 170°C et de manière encore préférentielle à une température qui ne dépasse pas 120°C jusqu'à la formation d'une solution limpide contenant les éléments précurseurs des entités zéolithiques constituant les parois cristallisées de la matrice de chacune des particules sphériques du matériau selon l'invention. Selon un mode opératoire préféré, le mélange réactionnel renfermant au moins un agent structurant, au moins un précurseur silicique et éventuellement au moins un précurseur d'au moins un élément X choisi parmi l'aluminium, le fer, le bore, l'indium et le gallium est mûri à température ambiante de façon à obtenir une solution limpide contenant les éléments précurseurs de germes de zéolithes susceptibles de générer la formation d'entités zéolithiques cristallisées au cours de l'étape e) d'autoclavage du procédé de préparation du matériau selon l'invention.The clear solution containing the zeolite entity precursor elements according to step a) of the process for preparing the material according to the invention is generally obtained by preparing a reaction mixture containing at least one silicic precursor, optionally at least one precursor of at least one precursor. at least one element X selected from aluminum, iron, boron, indium and gallium, preferably at least one aluminum precursor, and at least one structuring agent. The reaction mixture is either aqueous or aquo-organic, by example a water-alcohol mixture. It is preferred to work in a basic reaction medium during the various steps of the process according to the invention in order to promote the development of the zeolite entities constituting the crystallized walls of the matrix of each of the particles of the material according to the invention. The basicity of the solution is advantageously ensured by the basicity of the structuring agent used or by basification of the reaction mixture by the addition of a basic compound, for example an alkali metal hydroxide, preferably sodium hydroxide. . The reaction mixture may be placed under hydrothermal conditions under autogenous pressure, optionally by adding a gas, for example nitrogen, at a temperature between room temperature and 200 ° C., preferably between ambient temperature and 170 ° C. and still more preferably at a temperature which does not exceed 120 ° C. until the formation of a clear solution containing the precursor elements of the zeolite entities constituting the crystallized walls of the matrix of each of the spherical particles of the material according to the invention . According to a preferred procedure, the reaction mixture containing at least one structuring agent, at least one silicic precursor and optionally at least one precursor of at least one element X selected from aluminum, iron, boron, indium and the gallium is cured at ambient temperature so as to obtain a clear solution containing the precursor elements of zeolite seeds capable of generating the formation of crystallized zeolite entities during the step e) of autoclaving the process for preparing the material according to the invention.
Conformément à l'étape a) du procédé selon l'invention, les éléments précurseurs des entités zéolithiques présents dans la solution limpide sont synthétisés selon des protocoles opératoires connus de l'Homme du métier. En particulier, pour un matériau selon l'invention dont la matrice de chaque particule est constituée d'entités de zéolithe bêta, une solution limpide contenant des éléments précurseurs d'entités de zéolithe bêta est réalisée à partir du protocole opératoire décrit par
Conformément à l'étape b) du procédé de préparation du matériau selon l'invention, le tensioactif utilisé est un tensioactif ionique ou non ionique ou un mélange des deux. De préférence, le tensioactif ionique est choisi parmi des tensioactifs anioniques tels que les sulfates comme par exemple le dodécylsulfate de sodium (SDS). De préférence, le tensioactif non ionique peut être tout copolymère possédant au moins deux parties de polarités différentes leur conférant des propriétés de macromolécules amphiphiles. Ces copolymères peuvent faire partie de la liste non exhaustive des familles de copolymères suivantes : les copolymères fluorés (-[CH2-CH2-CH2-CH2-O-CO-R1- avec R1 = C4F9, C8F17, etc.), les copolymères biologiques comme les polyacides aminés (poly-lysine, alginates, etc.), les dendrimères, les copolymères bloc constitués de chaînes de poly(oxyde d'alkylène) et tout autre copolymère à caractère amphiphile connu de l'Homme du métier (
De manière préférée, on utilise dans le cadre de la présente invention un copolymère bloc constitué de chaînes de poly(oxyde d'alkylène). Ledit copolymère bloc est de préférence un copolymère bloc ayant deux, trois ou quatre blocs, chaque bloc étant constitué d'une chaîne de poly(oxyde d'alkylène). Pour un copolymère à deux blocs, l'un des blocs est constitué d'une chaîne de poly(oxyde d'alkylène) de nature hydrophile et l'autre bloc est constitué d'une chaîne de poly(oxyde d'alkylène) de nature hydrophobe. Pour un copolymère à trois blocs, deux des blocs sont constitués d'une chaîne de poly(oxyde d'alkylène) de nature hydrophile tandis que l'autre bloc, situé entre les deux blocs aux parties hydrophiles, est constitué d'une chaîne de poly(oxyde d'alkylène) de nature hydrophobe. De préférence, dans le cas d'un copolymère à trois blocs, les chaînes de poly(oxyde d'alkylène) de nature hydrophile sont des chaînes de poly(oxyde d'éthylène) notées (PEO)x et (PEO)z et les chaînes de poly(oxyde d'alkylène) de nature hydrophobe sont des chaînes de poly(oxyde de propylène) notées (PPO)y, des chaînes de poly(oxyde de butylène), ou des chaînes mixtes dont chaque chaîne est un mélange de plusieurs monomères d'oxyde d'alkylène. De manière très préférée, dans le cas d'un copolymère à trois blocs, on utilise un composé constitué de deux chaînes de poly(oxyde d'éthylène) et d'une chaîne de poly(oxyde de propylène)et plus particulièrement, il s'agit du composé de formule (PEO)x-(PPO)y-(PEO)z où x est compris entre 5 et 300 et y est compris entre 33 et 300 et z est compris entre 5 et 300. De préférence, les valeurs de x et z sont identiques. On utilise très avantageusement un composé dans lequel x = 20, y = 70 et z = 20 (P123) et un composé dans lequel x = 106, y = 70 et z = 106 (F127). Les tensioactifs non-ioniques commerciaux connus sous le nom de Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) sont utilisables en tant que tensioactifs non-ioniques dans l'étape b) du procédé de préparation de l'invention. Pour un copolymère à quatre blocs, deux des blocs sont constitués d'une chaîne de poly(oxyde d'alkylène) de nature hydrophile et les deux autres blocs sont constitués d'une chaîne de poly(oxyde d'alkylène) de nature hydrophobe.In the context of the present invention, a block copolymer consisting of poly (alkylene oxide) chains is preferably used. Said block copolymer is preferably a block copolymer having two, three or four blocks, each block consisting of a poly (alkylene oxide) chain. For a two-block copolymer, one of the blocks consists of a poly (alkylene oxide) chain of hydrophilic nature and the other block consists of a poly (alkylene oxide) chain of a nature hydrophobic. For a three-block copolymer, two of the blocks consist of a chain of poly (alkylene oxide) of hydrophilic nature while the other block, located between the two blocks with the hydrophilic parts, consists of a chain of poly (alkylene oxide) hydrophobic nature. Preferably, in the case of a three-block copolymer, the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains denoted (PEO) x and (PEO) z and the Poly (alkylene oxide) chains of hydrophobic nature are chains of poly (propylene oxide) denoted (PPO) y, poly (butylene oxide) chains, or mixed chains, each chain of which is a mixture of several alkylene oxide monomers. Very preferably, in the case of a three-block copolymer, a compound is used. consisting of two chains of poly (ethylene oxide) and a poly (propylene oxide) chain and more particularly, it is the compound of formula (PEO) x - (PPO) y - (PEO) z where x is between 5 and 300 and y is between 33 and 300 and z is between 5 and 300. Preferably, the values of x and z are the same. A compound is advantageously used in which x = 20, y = 70 and z = 20 (P123) and a compound in which x = 106, y = 70 and z = 106 (F127). Commercial nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) are useful as nonionic surfactants in step b ) of the preparation process of the invention. For a four-block copolymer, two of the blocks consist of a poly (alkylene oxide) chain of hydrophilic nature and the other two blocks consist of a chain of poly (alkylene oxide) hydrophobic nature.
La solution obtenue à l'issue de l'étape b) du procédé de préparation du matériau selon l'invention dans laquelle sont mélangés au moins ledit tensioactif et au moins ladite solution limpide obtenue selon l'étape a) peut être acide, neutre ou basique. De préférence, ladite solution est basique et présente de préférence un pH supérieur à 9, cette valeur du pH étant généralement imposée par le pH de la solution limpide contenant les éléments précurseurs d'entités zéolithiques obtenue selon l'étape a) du procédé de préparation du matériau selon l'invention. La solution obtenue à l'issue de l'étape b) peut être aqueuse ou peut être un mélange eau-solvant organique, le solvant organique étant préférentiellement un solvant polaire, notamment un alcool, préférentiellement de l'éthanol.The solution obtained at the end of step b) of the process for preparing the material according to the invention in which at least said surfactant and at least said clear solution obtained according to step a) are mixed can be acidic, neutral or basic. Preferably, said solution is basic and preferably has a pH greater than 9, this pH value being generally imposed by the pH of the clear solution containing the precursor elements of zeolitic entities obtained according to step a) of the preparation process of the material according to the invention. The solution obtained at the end of step b) may be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent, in particular an alcohol, preferably ethanol.
La quantité en tensioactif introduit dans le mélange conformément à l'étape b) du procédé de préparation selon l'invention est définie par rapport à la quantité de matière inorganique introduite dans ledit mélange lors de l'ajout de la solution limpide contenant les éléments précurseurs d'entités zéolithiques obtenue selon l'étape a) du procédé selon l'invention. La quantité de matière inorganique correspond à la quantité de matière du précurseur silicique et à celle du précurseur de l'élément X lorsqu'il est présent. Le rapport molaire inorganique. /nTensioactif est tel que le système binaire organique - inorganique formée lors de l'étape d'atomisation c) du procédé de préparation du matériau selon l'invention subisse une séparation de phase caractérisée par l'apparition d'un réseau biphasique interconnecté dont le mécanisme de formation est une décomposition spinodale. Le domaine de composition pour lequel se produit une séparation de phase par un mécanisme de décomposition spinodale est délimité par des bornes pour lesquelles l'enthalpie libre G du système binaire est minimisée (∂G/∂x = 0, x étant la fraction molaire de la phase organique, 1-x celle de la phase inorganique) et pour chaque composition appartenant à ce domaine, la dérivée seconde de l'enthalpie ∂2G/∂2x est supérieure à 0. Le principe de la séparation de phase via un mécanisme de décomposition spinodale a largement été décrit par Nakanishi pour l'obtention de gels de silice en présence de polymères (
L'étape d'atomisation du mélange selon l'étape c) du procédé de préparation selon l'invention produit des gouttelettes sphériques. La distribution en taille de ces gouttelettes est de type lognormale. Le générateur d'aérosol utilisé ici est un appareil commercial de modèle 9306 A fourni par TSI ayant un atomiseur 6 jets. L'atomisation de la solution se fait dans une chambre dans laquelle est envoyé un gaz vecteur, un mélange O2/N2 (air sec), sous une pression P égale à 1,5 bar.The step of atomizing the mixture according to step c) of the preparation process according to the invention produces spherical droplets. The size distribution of these droplets is lognormal. The aerosol generator used here is a commercial model 9306A device provided by TSI having a 6-jet atomizer. The atomization of the solution is done in a chamber into which a carrier gas, a mixture O 2 / N 2 (dry air), is sent under a pressure P equal to 1.5 bar.
Conformément à l'étape d) du procédé de préparation selon l'invention, on procède au séchage desdites gouttelettes. Ce séchage est réalisé par le transport desdites gouttelettes via le gaz vecteur, le mélange O2/N2, dans des tubes en PVC, ce qui conduit à l'évaporation progressive de la solution, par exemple de la solution aquo-organique basique obtenue au cours de l'étape b) du procédé de préparation du matériau selon l'invention, et ainsi à l'obtention de particules élémentaires sphériques. Ce séchage est parfait par un passage desdites particules dans un four dont la température peut être ajustée, la gamme habituelle de température variant de 50 à 600°C et de préférence de 80 à 400°C, le temps de résidence de ces particules dans le four étant de l'ordre de la seconde. Les particules sont alors récoltées dans un filtre. Une pompe placée en fin de circuit favorise l'acheminement des espèces dans le dispositif expérimental aérosol. Le séchage des gouttelettes selon l'étape d) du procédé selon l'invention est avantageusement suivi d'un passage à l'étuve à une température comprise entre 50 et 150°C.According to step d) of the preparation process according to the invention, said droplets are dried. This drying is carried out by transporting said droplets via the carrier gas, the O 2 / N 2 mixture, in PVC tubes, which leads to the gradual evaporation of the solution, for example from the basic aqueous-organic solution obtained. during step b) of the process for preparing the material according to the invention, and thus obtaining spherical elementary particles. This drying is perfect by a passage of said particles in an oven whose temperature can be adjusted, the usual range of temperature ranging from 50 to 600 ° C and preferably from 80 to 400 ° C, the residence time of these particles in the oven being of the order of the second. The particles are then harvested in a filter. A pump placed at the end of the circuit promotes the routing of species in the aerosol experimental device. Drying the droplets according to step d) of the process according to the invention is advantageously followed by a passage in the oven at a temperature between 50 and 150 ° C.
Conformément à l'étape e) du procédé selon l'invention, on procède à un autoclavage des particules séchées obtenues selon l'étape d) du procédé selon l'invention en présence d'un solvant. Cette étape consiste à placer lesdites particules dans une enceinte fermée en présence d'un solvant à une température donnée de façon à travailler en pression autogène inhérente aux conditions opératoires choisies. Le solvant utilisé est un solvant polaire protique. De préférence le solvant utilisé est de l'eau. Le volume de solvant introduit est défini par rapport au volume de l'autoclave choisi. Ainsi le volume de solvant introduit est compris dans une gamme de 0,01 à 20% par rapport au volume de l'autoclave choisi, de préférence dans une gamme de 0,05 à 5% et de façon préférée dans une gamme de 0,05 à 1 %. La température d'autoclavage est comprise entre 50 et 200°C, de préférence comprise entre 60 et 170°C et de manière encore préférentielle comprise entre 60 et 120°C de façon à permettre la croissance d'entités zéolithiques dans les parois de la matrice de chacune des particules du matériau selon l'invention sans générer de cristaux de zéolithe de taille trop importante qui désorganiseraient la mésoporosité et la macroporosité créées au sein de chaque particule du matériau selon l'invention. L'autoclavage est maintenu sur une période de 1 à 96 heures et de préférence sur une période de 20 à 50 heures.According to step e) of the process according to the invention, the dried particles obtained according to step d) of the process according to the invention are autoclaved in the presence of a solvent. This step consists in placing said particles in a closed chamber in the presence of a solvent at a given temperature so as to work with autogenous pressure inherent to the operating conditions chosen. The solvent used is a protic polar solvent. Preferably the solvent used is water. The volume of solvent introduced is defined relative to the volume of the autoclave selected. Thus the volume of solvent introduced is in a range of 0.01 to 20% relative to the volume of the autoclave chosen, preferably in a range of 0.05 to 5% and preferably in a range of 0, 05 to 1%. The autoclaving temperature is between 50 and 200 ° C, preferably between 60 and 170 ° C and more preferably between 60 and 120 ° C so as to allow the growth of zeolite entities in the walls of the matrix of each of the particles of the material according to the invention without generating large size zeolite crystals which would disorganize the mesoporosity and macroporosity created within each particle of the material according to the invention. Autoclaving is maintained over a period of 1 to 96 hours and preferably over a period of 20 to 50 hours.
Conformément à l'étape f) du procédé de préparation selon l'invention, le séchage des particules après autoclavage est avantageusement réalisé par une mise à l'étuve à une température comprise entre 50 et 150°C.According to step f) of the preparation process according to the invention, the drying of the particles after autoclaving is advantageously carried out by placing in an oven at a temperature of between 50 and 150 ° C.
Dans le cas particulier où l'élément X, éventuellement utilisé pour la mise en oeuvre de l'étape a) du procédé selon l'invention, est l'élément aluminium et où l'élément sodium est présent dans la solution limpide obtenue conformément à l'étape a) du procédé selon l'invention via l'emploi de l'hydroxyde de sodium et/ou d'un agent structurant sodé assurant la basicité de ladite solution limpide, il est préféré de réaliser une étape supplémentaire d'échange ionique permettant d'échanger le cation Na+ par le cation NH4 + entre les étapes f) et g) du procédé selon l'invention. Cet échange, qui conduit à la formation de protons H+ après l'étape g) du procédé selon l'invention dans le cas préféré où l'élimination de l'agent structurant et du tensioactif est réalisée par calcination sous air, est réalisé selon des protocoles opératoires bien connus de l'Homme du métier. Une des méthodes usuelles consiste à mettre en suspension les particules solides séchées issues de l'étape f) du procédé selon l'invention dans une solution aqueuse de nitrate d'ammonium. L'ensemble est ensuite porté à reflux pendant une durée de 1 à 6 heures. Les particules sont alors récupérées par filtration (centrifugation 9000 tr/mn), lavées puis séchées par passage à l'étuve à une température comprise entre 50 et 150°C. Ce cycle d'échange ionique/lavage/séchage peut être reconduit plusieurs fois et de préférence deux autres fois. Ce cycle d'échange peut être également réalisé après les étapes f) et g) du procédé selon l'invention. Dans ces conditions, l'étape g) est alors reproduite après le dernier cycle d'échange de façon à générer les protons H+ comme explicité ci-dessus.In the particular case where the element X, optionally used for the implementation of step a) of the process according to the invention, is the aluminum element and where the sodium element is present in the clear solution obtained in accordance with step a) of the process according to the invention via the use of sodium hydroxide and / or a sodic structuring agent ensuring the basicity of said clear solution, it is preferred to carry out an additional ion exchange step allowing the exchange of the Na + cation by the NH 4 + cation between steps f) and g) of the process according to the invention. This exchange, which leads to the formation of protons H + after step g) of the process according to the invention in the preferred case where the removal of the structuring agent and the surfactant is carried out by calcination under air, is carried out according to operating protocols well known to those skilled in the art. One of the usual methods consists in suspending the dried solid particles from step f) of the process according to the invention in an aqueous solution of ammonium nitrate. The whole is then refluxed for 1 to 6 hours. The particles are then recovered by filtration (centrifugation at 9000 rpm), washed and then dried by passing in an oven at a temperature between 50 and 150 ° C. This ion exchange / washing / drying cycle can be repeated several times and preferably two more times. This exchange cycle can also be performed after steps f) and g) of the process according to the invention. Under these conditions, step g) is then reproduced after the last exchange cycle so as to generate H + protons as explained above.
Conformément à l'étape g) du procédé de préparation selon l'invention, l'élimination de l'agent structurant et du tensioactif, afin d'obtenir le matériau selon l'invention à porosité hiérarchisée, est avantageusement réalisée par des procédés d'extraction chimique ou par traitement thermique et de préférence par calcination sous air dans une gamme de température de 300 à 1000°C et plus précisément dans une gamme de 400 à 600°C pendant une durée de 1 à 24 heures et de façon préférée pendant une durée de 2 à 12 heures.According to step g) of the preparation process according to the invention, the elimination of the structuring agent and the surfactant, in order to obtain the material according to the invention with hierarchical porosity, is advantageously carried out by processes of chemical extraction or by heat treatment and preferably by calcination in air in a temperature range of 300 to 1000 ° C and more precisely in a range of 400 to 600 ° C for a period of 1 to 24 hours and preferably during a duration of 2 to 12 hours.
Dans le cas où la solution visée à l'étape b) du procédé de préparation selon l'invention est un mélange eau-solvant organique, de préférence basique, il est essentiel au cours de l'étape b) du procédé de préparation selon l'invention que la concentration en tensioactif soit inférieure à la concentration micellaire critique et que le rapport nInorganique/nTensioactif soit tel que la variation de l'enthalpie libre de mélange ΔGm et la dérivée seconde de l'enthalpie libre ∂2G/∂2x soient supérieures à 0 de sorte que l'évaporation de ladite solution aquo-organique, préférentiellement basique, au cours de l'étape c) du procédé de préparation selon l'invention par la technique d'aérosol induise un phénomène de séparation des phases organique et inorganique par décomposition spinodale conduisant à la génération des phases mésoporeuse et macroporeuse des particules sphériques du matériau selon l'invention. Ladite séparation de phase observée est consécutive à une concentration progressive, au sein de chaque gouttelette, du précurseur silicique, éventuellement du précurseur de l'élément X, de préférence du précurseur aluminique et du tensioactif résultant d'une évaporation de la solution aquo-organique, préférentiellement basique, jusqu'à une concentration en réactifs suffisante pour provoquer ledit phénomène.In the case where the solution referred to in step b) of the preparation process according to the invention is a water-organic solvent mixture, preferably a basic one, it is essential during step b) of the preparation process according to the invention. It is an object of the present invention that the surfactant concentration is less than the critical micellar concentration and that the n- inorganic ratio of the surfactant is such that the variation of the free mixture enthalpy ΔG m and the second derivative of the free enthalpy ∂ 2 G / ∂ 2 x are greater than 0 so that the evaporation of said aqueous-organic solution, preferably basic, during step c) of the preparation process according to the invention by the aerosol technique induces a separation phenomenon organic and inorganic phases by spinodal decomposition leading to the generation of the mesoporous and macroporous phases of the spherical particles of the material according to the invention. Said phase separation observed is consecutive to a progressive concentration, within each droplet, of the silicic precursor, optionally of the precursor of the element X, preferably of the aluminum precursor and of the surfactant resulting from evaporation of the aqueous-organic solution preferentially basic, until a concentration of reagents sufficient to cause said phenomenon.
Le matériau à porosité hiérarchisée de la présente invention peut être obtenu sous forme de poudre, de billes, de pastilles, de granulés, ou d'extrudés, les opérations de mises en forme étant réalisées par les techniques classiques connues de l'homme du métier. De préférence, le matériau à porosité hiérarchisée selon l'invention est obtenu sous forme de poudre, laquelle est constituée de particules sphériques élémentaires ayant un diamètre maximal de 200 µm, ce qui facilite la diffusion éventuelle des réactifs dans le cas de l'emploi du matériau selon l'invention dans une application industrielle potentielle.The hierarchically porous material of the present invention can be obtained in the form of powder, beads, pellets, granules, or extrusions, the shaping operations being carried out by conventional techniques known to those skilled in the art. . Preferably, the material having a hierarchical porosity according to the invention is obtained in the form of a powder, which consists of elementary spherical particles having a maximum diameter of 200 microns, which facilitates the possible diffusion of the reagents in the case of the use of the material according to the invention in a potential industrial application.
Le matériau de l'invention à porosité hiérarchisée est caractérisé par plusieurs techniques d'analyses et notamment par diffraction des rayons X aux grands angles (DRX), par volumétrie à l'azote (BET), par porosimétrie au mercure, par microscopie électronique à transmission (MET), par microscopie électronique à balayage (MEB) et par fluorescence X (FX).The material of the invention with hierarchical porosity is characterized by several analysis techniques and in particular by large-angle X-ray diffraction (XRD), by nitrogen volumetry (BET), by mercury porosimetry, by electron microscopy. transmission (TEM), scanning electron microscopy (SEM) and X-ray fluorescence (FX).
La technique de diffraction des rayons X aux grands angles (valeurs de l'angle 2θ comprises entre 5 et 70°) permet de caractériser un solide cristallisé défini par la répétition d'un motif unitaire ou maille élémentaire à l'échelle moléculaire. Dans l'exposé qui suit, l'analyse des rayons X est réalisée sur poudre avec un diffractomètre opérant en réflexion et équipé d'un monochromateur arrière en utilisant la radiation du cuivre (longueur d'onde de 1,5406 A). Les pics habituellement observés sur les diffractogrammes correspondants à une valeur donnée de l'angle 2θ sont associés aux distances inter-réticulaires d(hkl) caractéristiques de la (des) symétrie(s) structurale(s) du matériau, ((hkl) étant les indices de Miller du réseau réciproque) par la relation de Bragg : 2 d (hkl) * sin (θ) = n * λ. Cette indexation permet alors la détermination des paramètres de maille (abc) du réseau direct. L'analyse DRX aux grands angles est donc adaptée à la caractérisation structurale des entités zéolithiques constitutives de la paroi cristallisée de la matrice de chacune des particules sphériques élémentaires constituant le matériau selon l'invention. En particulier, elle permet d'accéder à la taille des pores des entités zéolithiques. Pour exemple, le diffractogramme de rayons X aux grands angles d'un matériau à porosité mésoporeuse et macroporeuse, dont les parois microporeuses de la matrice de chacune des particules sphériques sont constituées d'entités de zéolithe ZSM-5 (MFI), obtenu selon le procédé selon l'invention en utilisant du TEOS comme précurseur silicique; Al(OsC4H9)3 comme précurseur aluminique, TPAOH comme agent structurant et le copolymère à bloc particulier dénommé poly(oxyde d'éthylène)106-poly(oxyde de propylène)70-poly(oxyde d'éthylène)106 (PEO106-PPO70-PEO106 ou F127) comme tensioactif présente le diffractogramme associé au groupe de symétrie Pnma (N°62) de la zéolithe ZSM-5 aux grands angles. La valeur de l'angle obtenue sur le diffractogramme RX permet de remonter à la distance de corrélation d selon la loi de Bragg : 2 d * sin (θ) = n * λ. Les valeurs des paramètres de maille a, b, c (a = 20,1 Å , b = 19,7 Å et c = 13,1 Å) obtenues pour la caractérisation des entités zéolithiques sont cohérentes avec les valeurs obtenues pour une zéolithe ZSM-5 (type structural MFI) bien connues de l'homme de l'art ("
La volumétrie à l'azote qui correspond à l'adsorption physique de molécules d'azote dans la porosité du matériau via une augmentation progressive de la pression à température constante renseigne sur les caractéristiques texturales (diamètre de pores, type de porosité, surface spécifique) particulières du matériau obtenu selon le procédé de l'invention. En particulier, elle permet d'accéder à la valeur totale du volume microporeux et mésoporeux du matériau. L'allure de l'isotherme d'adsorption d'azote et de la boucle d'hystérésis peut renseigner sur la présence de la microporosité liée aux entités zéolithiques constitutives des parois cristallisées de la matrice de chacune des particules sphériques du matériau selon l'invention et sur la nature de la mésoporosité. L'analyse quantitative de la microporosité du matériau selon l'invention est effectuée à partir des méthodes "t" (méthode de Lippens-De Boer, 1965) ou "αs" (méthode proposée par Sing) qui correspondent à des transformées de l'isotherme d'adsorption de départ comme décrit dans l'ouvrage "
L'analyse porosimétrie au mercure correspond à l'intrusion d'un volume de mercure caractéristique de l'existence de mésopores et de macropores dans le matériau selon l'invention selon la norme ASTM D4284-83 à une pression maximale de 4000 bars, utilisant une tension de surface de 484 dyne/cm, et un angle de contact de 140° (valeur choisie suivant les recommandations de l'ouvrage "
L'analyse par microscopie électronique par transmission (MET) est une technique également largement utilisée pour caractériser la mésoporosité et la macroporosité du matériau selon l'invention. Celle-ci permet la formation d'une image du solide étudié, les contrastes observés étant caractéristiques de l'organisation structurale, de la texture, de la morphologie ou bien de la composition chimique des particules observées, la résolution de la technique atteignant au maximum 0,2 nm. Dans l'exposé qui suit, les photos MET seront réalisées à partir dé sections microtomes de l'échantillon afin de visualiser une section d'une particule sphérique élémentaire du matériau selon l'invention. Pour exemple, les images MET obtenues pour un matériau à porosité mésoporeuse et macroporeuse dont les parois microporeuses sont constituées d'entités de zéolithe ZSM-5 (MFI) obtenu selon le procédé de préparation selon l'invention en utilisant du TEOS comme précurseur silicique, Al(OsC4H9)3 comme précurseur aluminique, TPAOH comme agent structurant et le copolymère à bloc particulier dénommé poly(oxyde d'éthylène)106-Poly(oxyde de propylène)70-poly(oxyde d'éthylène)106 (PEO106-PPO70-PEO106 ou F127) comme tensioactif présentent au sein d'une même particule sphérique une mésoporosité et une macroporosité caractéristiques d'une séparation de phase organique - inorganique par un mécanisme de décomposition spinodale consécutive à l'étape c) d'atomisation du procédé de préparation du matériau selon l'invention dont la taille des domaines est respectivement comprise dans une gamme de 15 à 50 nm et dans une gamme de 100 à 500 nm. L'analyse de l'image permet également de visualiser la présence des entités zéolithiques constitutives des parois du matériau selon l'invention.Transmission electron microscopy (TEM) analysis is a technique also widely used to characterize the mesoporosity and macroporosity of the material according to the invention. This allows the formation of an image of the studied solid, the observed contrasts being characteristic of the structural organization, the texture, the morphology or the chemical composition of the particles observed, the resolution of the technique reaching the maximum 0.2 nm. In the following description, the TEM photos will be made from microtome sections of the sample in order to visualize a section of an elementary spherical particle of the material according to the invention. For example, the MET images obtained for a mesoporous and macroporous porosity material whose walls microporous particles consist of zeolite entities ZSM-5 (MFI) obtained according to the preparation method according to the invention using TEOS as silicic precursor, Al (O s C 4 H 9 ) 3 as an aluminum precursor, TPAOH as structuring agent and the particular block copolymer designated poly (ethylene oxide) 106 - P oly (propylene oxide) 70- poly (ethylene oxide) 106 (PEO 106 -PPO 70 -PEO 106 or F127) as surfactant have within of the same spherical particle, a mesoporosity and a macroporosity characteristic of an organic-inorganic phase separation by a spinodal decomposition mechanism subsequent to the atomization stage c) of the process for preparing the material according to the invention, the size of which domains is respectively in a range of 15 to 50 nm and in a range of 100 to 500 nm. The analysis of the image also makes it possible to visualize the presence of the zeolite entities constituting the walls of the material according to the invention.
La morphologie et la distribution en taille des particules élémentaires ont été établies par analyse de photos obtenues par microscopie électronique à balayage (MEB).The morphology and size distribution of the elementary particles were established by scanning electron microscopy (SEM) photo analysis.
La présente invention concerne aussi l'utilisation du matériau à porosité hiérarchisé selon l'invention comme adsorbant pour le contrôle de la pollution ou comme tamis moléculaire pour la séparation. La présente invention a donc également pour objet un adsorbant comprenant le matériau à porosité hiérarchisé selon l'invention. Il est également avantageusement utilisé comme solide acide pour catalyser des réactions, par exemple celles intervenant dans les domaines du raffinage et de la pétrochimie.The present invention also relates to the use of the hierarchically porous material according to the invention as an adsorbent for the control of pollution or as a molecular sieve for separation. The present invention therefore also relates to an adsorbent comprising the hierarchically porous material according to the invention. It is also advantageously used as an acid solid to catalyze reactions, for example those involved in the fields of refining and petrochemistry.
Lorsque le matériau à porosité hiérarchisé selon l'invention est utilisé comme catalyseur, ce matériau peut être associé à une matrice inorganique qui peut être inerte ou catalytiquement active et à une phase métallique. La matrice inorganique peut être présente simplement comme liant pour maintenir ensemble les particules dudit matériau sous les différentes formes connues des catalyseurs (extrudés, pastilles, billes, poudres) ou bien peut être ajoutée comme diluant pour imposer le degré de conversion dans un procédé qui sinon progresserait à une allure trop rapide, conduisant à un encrassement du catalyseur en conséquence d'une formation importante de coke. Des matrices inorganiques typiques sont notamment des matières de support pour les catalyseurs comme les différentes formes de silice, d'alumine, de silice-alumine, la magnésie, la zircone, les oxydes de titane, de bore, les phosphates d'aluminium, de titane, de zirconium, les argiles telles que le kaolin, la bentonite, la montmorillonite, la sépiolite, l'attapulgite, la terre à foulon, les matières poreuses synthétiques comme SiO2-Al2O3, SiO2-ZrO2, SiO2-ThO2, SiO2-BeO SiO2-TiO2 ou toute combinaison de ces composés. La matrice inorganique peut être un mélange de différents composés, en particulier d'une phase inerte et d'une phase active. Ledit matériau de la présente invention peut aussi être associé à au moins une zéolithe et jouer le rôle de phase active principale ou d'additif. La phase métallique peut être introduite intégralement sur ledit matériau de l'invention. Elle peut être également introduite intégralement sur la matrice inorganique ou encore sur l'ensemble matrice inorganique - matériau à porosité hiérarchisée par échange d'ions ou imprégnation avec des cations ou oxydes choisis parmi les éléments suivants : Cu, Ag, Ga, Mg, Ca, Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir et tout autre élément de la classification périodique des éléments.When the hierarchically porous material according to the invention is used as a catalyst, this material may be associated with an inorganic matrix which may be inert or catalytically active and with a metallic phase. The inorganic matrix may be present simply as a binder to hold together the particles of said material in the various known forms of the catalysts (extrudates, pellets, beads, powders) or may be added as a diluent to impose the degree of conversion in a process which otherwise would progress at too fast a rate, leading to clogging of the catalyst as a result of a significant formation of coke. Typical inorganic matrices are, in particular, support materials for catalysts, such as the various forms of silica, alumina, silica-alumina, magnesia, zirconia, titanium oxides, boron oxides, aluminum phosphates, titanium, zirconium, clays such as kaolin, bentonite, montmorillonite, sepiolite, attapulgite, fuller's earth, synthetic porous materials such as SiO 2 -Al 2 O 3 , SiO 2 -ZrO 2 , SiO 2 -ThO 2 , SiO 2 -BeO SiO 2 -TiO 2 or any combination of these compounds. The inorganic matrix may be a mixture of different compounds, in particular an inert phase and an active phase. Said material of the present invention may also be associated with at least one zeolite and play the role of main active phase or additive. The metal phase can be introduced integrally on said material of the invention. It may also be introduced integrally onto the inorganic matrix or onto the inorganic matrix-ionized porosity hierarchical material or impregnation with cations or oxides chosen from the following elements: Cu, Ag, Ga, Mg, Ca , Sr, Zn, Cd, B, Al, Sn, Pb, V, P, Sb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and all other element of the periodic table of elements.
Les compositions catalytiques comportant le matériau de la présente invention conviennent de façon générale à la mise en oeuvre des principaux procédés de transformation des hydrocarbures et des réactions de synthèse de composés organiques.The catalyst compositions comprising the material of the present invention are generally suitable for carrying out the main hydrocarbon conversion processes and organic compound synthesis reactions.
Les compositions catalytiques comportant le matériau de l'invention trouvent avantageusement leur application dans les réactions d'isomérisation, de transalkylation et de dismutation, d'alkylation et de désalkylation, d'hydratation et de déshydratation, d'oligomérisation et de polymérisation, de cyclisation, d'aromatisation, de craquage, de reformage, d'hydrogénation et de déshydrogénation, d'oxydation, d'halogénation, d'hydrocraquage, d'hydroconversion, d'hydrotraitement, d'hydrodésulfuration et d'hydrodéazotation, d'élimination catalytique des oxydes d'azote, les dites réactions impliquant des charges comprenant des hydrocarbures aliphatiques saturés et insaturés, des hydrocarbures aromatiques, des composés organiques oxygénés et des composés organiques contenant de l'azote et/ou du soufre ainsi que des composés organiques contenant d'autres groupes fonctionnels.The catalyst compositions comprising the material of the invention advantageously find their application in isomerization, transalkylation and disproportionation, alkylation and dealkylation, hydration and dehydration, oligomerization and polymerization, cyclization reactions. , aromatization, cracking, reforming, hydrogenation and dehydrogenation, oxidation, halogenation, hydrocracking, hydroconversion, hydrotreatment, hydrodesulfurization and hydrodenitrogenation, catalytic removal nitrogen oxides, said reactions involving fillers comprising saturated and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated organic compounds and organic compounds containing nitrogen and / or sulfur as well as organic compounds containing other functional groups.
L'invention est illustrée au moyen des exemples suivants.The invention is illustrated by means of the following examples.
Dans les exemples qui suivent, la technique aérosol utilisée est celle décrite ci-dessus dans l'exposé de l'invention.In the examples which follow, the aerosol technique used is that described above in the description of the invention.
Pour chacun des exemples ci-dessous, on calcule le rapport Vinorganique/Vorganique du mélange issu de l'étape b). Ce rapport est défini comme suit : V inorganique/Vorganique = (minorg * ρorg) / (morg *ρinorg) avec minorg la masse finale de la fraction inorganique sous forme d'oxyde(s) condensé(s), à savoir SiO2 et AlO2, dans la particule élémentaire solide, morg la masse totale de la faction organique non volatile se retrouvant dans la particule élémentaire solide, à savoir le tensioactif et l'agent structurant, ρorg et ρinorg les densités respectivement associées aux fractions organique non volatile et inorganique. Dans les exemples qui suivent, on considère que ρorg = 1 et ρinorg = 2. Aussi le rapport Vinorganique/Vorganique est calculé comme étant égal à Vinorganique/Norganique = (MSiO2 + mAlO2) [2*(magent structurant + Mtensioactif)]. L'éthanol, la soude, l'eau n'entrent pas en compte dans le calcul dudit rapport Vinorganique/Norganique.For each of the examples below, the ratio V inorganic / V organic of the mixture resulting from step b) is calculated. This ratio is defined as follows: inorganic V / organic V = (m inorg * ρ org ) / (m org * ρ inorg ) with m inorg the final mass of the inorganic fraction in oxide form (s) condensed (s), namely SiO 2 and AlO 2 , in the solid elementary particle, m org the total mass of the nonvolatile organic fraction found in the solid elementary particle, namely the surfactant and the structuring agent, ρ org and ρ inorg the densities respectively associated with the nonvolatile and inorganic organic fractions. In the following examples, it is considered that ρ org = 1 and ρ inorg = 2. Also the ratio V inorganic / V organic is calculated as being equal to V inorganic / N organic = (M SiO2 + m AlO2 ) [2 * ( m structuring agent + M surfactant )]. Ethanol, sodium hydroxide and water are not taken into account in the calculation of said inorganic V / organic N ratio.
10,05 g d'une solution d'hydroxyde de tétrapropylammonium (TPAOH 20% en masse dans une solution aqueuse) sont ajoutés à 4,3 g d'eau déminéralisée et 9,2 mg d'hydroxyde de sodium NaOH. Le tout est laissé sous agitation pendant 10 minutes. 0,14 g de sec-butoxyde d'aluminium (Al(OsC4H9)3 sont alors introduits. L'hydrolyse du précurseur aluminique est réalisée pendant 1 heure. 6 g de tétraéthylorthosilicate (TEOS) sont alors ajoutés. Le tout est maintenu sous agitation pendant 18 heures à température ambiante de manière à obtenir une solution limpide. 18 ml de cette solution sont alors ajoutés à une solution contenant 35,2 g d'éthanol, 11,3 g d'eau et 2 g de tensioactif F127 (pH du mélange = 10,5). Le rapport Vinorganique/Norganique du mélange est égal à 0,20 et est calculé comme décrit ci-dessus. Le tout est laissé sous agitation pendant 10 minutes. L'ensemble est envoyé dans la chambre d'atomisation du générateur d'aérosol tel qu'il a été décrit dans la description ci-dessus et la solution est pulvérisée sous la forme de fines gouttelettes sous l'action du gaz vecteur (air sec) introduit sous pression (P = 1,5 bar). Les gouttelettes sont séchées selon le protocole décrit dans l'exposé de l'invention ci-dessus : elles sont acheminées via un mélange O2/N2 dans des tubes en PVC. Elles sont ensuite introduites dans un four réglé à une température de 250°C pour parfaire leur séchage pendant une durée de l'ordre de la seconde. La poudre récoltée est alors séchée 12 heures à l'étuve à 95°C. 10 mg de poudre sont alors placés dans un autoclave de 100 ml (enceinte fermée susceptible de résister à des températures de l'ordre de 200°C et des pressions de l'ordre de 5 bars) en présence de 100 µl d'eau déminéralisée. L'autoclave est muni d'un système de "panier" ou de "cellule" permettant à la poudre de ne pas être en contact direct avec l'eau introduite tout en baignant dans la vapeur d'eau. L'autoclave est ensuite porté à une température de 95°C pendant 48 heures. La poudre récupérée est ensuite séchée à l'étuve à 95°C pendant 12 heures. La poudre est alors calcinée sous air pendant 5 h à T = 550°C. Le solide est caractérisé par DRX, par Volumétrie à l'azote, par porosimétrie au mercure, par MET, par MEB, par FX. L'analyse MET montre que les particules sphériques constitutives du matériau présentent une macroporosité de coeur caractérisée par des domaines de 300 à 500 nm de long et de 100 à 200 nm de large et une mésoporosité en périphérie des particules caractérisée par des domaines de 20 à 50 nm, l'ensemble étant caractéristique d'une séparation de phase organique - inorganique obtenue par un mécanisme de décomposition spinodale présente avant l'étape de calcination. La présence d'entités zéolithiques dans les parois du matériau est également clairement visible lors de l'étude par diffraction électronique des coupes michrotomées d'une épaisseur de l'ordre de 70 nm sur des zones localisées de l'ordre de 100 nm. L'analyse par volumétrie à l'azote combinée à l'analyse par la méthode αs conduit à une valeur du volume microporeux Vmicro de 0,26 ml/g (N2) , une valeur du volume mésoporeux Vméso de 0,6 ml/g (N2) et une surface spécifique du matériau final de S = 690 m2/g. Le volume mercure macroporeux défini par porosimétrie au mercure est de 0,5 ml/g (la valeur du volume mercure mésoporeux également obtenue par porosimétrie au mercure est en parfait accord avec la valeur obtenue par volumétrie à l'azote). L'analyse DRX aux grands angles conduit à l'obtention du diffractogramme caractéristique de la zéolithe ZSM-5 (taille des micopores, mesurée par DRX, de l'ordre de 0,55 nm). Le rapport molaire Si/Al obtenu par FX est de 50. Un cliché MEB des particules élémentaires sphériques ainsi obtenues indique que ces particules ont une taille caractérisée par un diamètre variant de 50 à 700 nm, la distribution en taille de ces particules étant centrée autour de 300 nm.10.05 g of a solution of tetrapropylammonium hydroxide (TPAOH 20% by weight in an aqueous solution) are added to 4.3 g of demineralized water and 9.2 mg of sodium hydroxide NaOH. The whole is left stirring for 10 minutes. 0.14 g of aluminum sec-butoxide (Al (O s C 4 H 9 ) 3 are then introduced, the hydrolysis of the aluminum precursor is carried out for 1 hour, 6 g of tetraethylorthosilicate (TEOS) are then added. all is stirred for 18 hours at room temperature so as to obtain a clear solution, 18 ml of this solution are then added to a solution containing 35.2 g of ethanol, 11.3 g of water and 2 g of water. surfactant F127 (pH of the mixture = 10.5) The inorganic V / organic N ratio of the mixture is equal to 0.20 and is calculated as described above, the whole is left stirring for 10 minutes. sent to the atomization chamber of the aerosol generator as described in the description above and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air) introduced under pressure (P = 1.5 bar) The droplets are dried according to the protocol described in According to the invention above, they are conveyed via an O 2 / N 2 mixture into PVC tubes. They are then introduced into an oven set at a temperature of 250 ° C to complete their drying for a period of about one second. The harvested powder is then dried for 12 hours in an oven at 95 ° C. 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C. and pressures of the order of 5 bars) in the presence of 100 μl of demineralised water . The autoclave is provided with a system of "basket" or "cell" allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor. The autoclave is then heated to a temperature of 95 ° C for 48 hours. hours. The recovered powder is then dried in an oven at 95 ° C. for 12 hours. The powder is then calcined under air for 5 hours at T = 550 ° C. The solid is characterized by XRD, nitrogen volumetry, mercury porosimetry, TEM, SEM, FX. The TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the set being characteristic of an organic-inorganic phase separation obtained by a spinodal decomposition mechanism present before the calcination step. The presence of zeolite entities in the walls of the material is also clearly visible during the study by electron diffraction of the michronotropic sections with a thickness of the order of 70 nm on localized areas of the order of 100 nm. Nitrogen volumetric analysis combined with analysis by the α s method leads to a microporous volume V micro value of 0.26 ml / g (N 2 ), a mesoporous V meso volume value of 0, 6 ml / g (N 2 ) and a specific surface area of the final material of S = 690 m 2 / g. The macroporous mercury volume defined by mercury porosimetry is 0.5 ml / g (the value of the mercury mercury volume also obtained by mercury porosimetry is in perfect agreement with the value obtained by nitrogen volumetry). The wide-angle XRD analysis leads to obtaining the diffractogram characteristic of the zeolite ZSM-5 (size of the micopores, measured by XRD, of the order of 0.55 nm). The molar Si / Al ratio obtained by FX is 50. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
10,05 g d'une solution d'hydroxyde de tetrapropylammonium (TPAOH 20% en masse dans une solution aqueuse) sont ajoutés à 4,3 g d'eau déminéralisée et 9,2 mg d'hydroxyde de sodium NaOH. Le tout est laissé sous agitation pendant 10 minutes. 6 g de tétraéthylorthosilicate (TEOS) sont alors ajoutés. Le tout est maintenu sous agitation pendant 18 heures à température ambiante de manière à obtenir une solution limpide. 18 ml de cette solution sont alors ajoutés à une solution contenant 35,2 g d'éthanol, 11,3 g d'eau et 2 g de tensioactif F127 (pH du mélange = 10,5). Le rapport Vinorganique/Vorganique du mélange est égal à 0,20 et est calculé comme décrit ci-dessus. Le tout est laissé sous agitation pendant 10 minutes. L'ensemble est envoyé dans la chambre d'atomisation du générateur d'aérosol tel qu'il a été décrit dans la description ci-dessus et la solution est pulvérisée sous la forme de fines gouttelettes sous l'action du gaz vecteur (air sec) introduit sous pression (P = 1,5 bar). Les gouttelettes sont séchées selon le protocole décrit dans l'exposé de l'invention ci-dessus : elles sont acheminées via un mélange O2/N2 dans des tubes en PVC. Elles sont ensuite introduites dans un four réglé à une température de séchage fixée à 250°C. La poudre récoltée est alors séchée 12 heures à l'étuve à 95°C. 10 mg de poudre sont alors placés dans un autoclave de 100 ml (enceinte fermée susceptible de résister à des températures de l'ordre de 200°C et des pressions de l'ordre de 5 bars) en présence de 100 µl d'eau déminéralisée. L'autoclave est muni d'un système de "panier" ou de "cellule" permettant à la poudre de ne pas être en contact direct avec l'eau introduite tout en baignant dans la vapeur d'eau. L'autoclave est ensuite porté à une température de 95°C pendant 36 heures. La poudre récupérée est ensuite séchée à l'étuve à 95°C pendant 12 heures. La poudre est alors calcinée sous air pendant 5 h à 550°C. Le solide est caractérisé par DRX, par Volumétrie à l'azote, par porosimétrie au mercure, par MET, par MEB. L'analyse MET montre que les particules sphériques constitutives du matériau présentent une macroporosité de coeur caractérisée par des domaines de 300 à 500 nm de long et de 100 à 200 nm de large et une mésoporosité en périphérie des particules caractérisée par des domaines de 20 à 50 nm, l'ensemble étant caractéristique d'une séparation de phase organique - inorganique obtenue par un mécanisme de décomposition spinodale présente avant l'étape de calcination. La présence d'entités zéolithiques dans les parois du matériau est également clairement visible lors de l'étude par diffraction électronique des coupes michrotomées d'une épaisseur de l'ordre de 70 nm sur des zones localisées de l'ordre de 100 nm. L'analyse par volumétrie à l'azote combinée à l'analyse par la méthode αs conduit à une valeur du volume microporeux Vmicro de 0,3 ml/g (N2), une valeur du volume mésoporeux Vméso de 0,6 ml/g (N2) et une surface spécifique du matériau final de S = 680 m2/g. Le volume mercure macroporeux défini par porosimétrie au mercure est de 0,5 ml/g (la valeur du volume mercure mésoporeux également obtenue est en parfait accord avec la valeur obtenue par volumétrie à l'azote). L'analyse DRX aux grands angles conduit à l'obtention du diffractogramme caractéristique de la zéolithe silicalite (taille des micropores, mesurée par DRX, de l'ordre de 0,55 nm). Un cliché MEB des particules élémentaires sphériques ainsi obtenues indique que ces particules ont une taille caractérisée par un diamètre variant de 50 à 700 nm, la distribution en taille de ces particules étant centrée autour de 300 nm.10.05 g of a solution of tetrapropylammonium hydroxide (TPAOH 20% by weight in an aqueous solution) are added to 4.3 g of demineralized water and 9.2 mg of sodium hydroxide NaOH. The whole is left stirring for 10 minutes. 6 g of tetraethylorthosilicate (TEOS) are then added. The whole is stirred for 18 hours at room temperature so as to obtain a clear solution. 18 ml of this solution are then added to a solution containing 35.2 g of ethanol, 11.3 g of water and 2 g of surfactant F127 (pH of the mixture = 10.5). The ratio V inorganic / V organic mixture is 0.20 and is calculated as described above. The whole is left stirring for 10 minutes. The assembly is sent into the atomization chamber of the aerosol generator as described in the description above and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air ) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O 2 / N 2 mixture in PVC tubes. They are then introduced into an oven set at a drying temperature set at 250 ° C. The harvested powder is then dried for 12 hours in an oven at 95 ° C. 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C. and pressures of the order of 5 bars) in the presence of 100 μl of demineralised water . The autoclave is provided with a system of "basket" or "cell" allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor. The autoclave is then heated to a temperature of 95 ° C for 36 hours. The recovered powder is then dried in an oven at 95 ° C. for 12 hours. The powder is then calcined under air for 5 hours at 550 ° C. The solid is characterized by XRD, nitrogen volumetry, mercury porosimetry, TEM, SEM. The TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the set being characteristic of an organic-inorganic phase separation obtained by a spinodal decomposition mechanism present before the calcination step. The presence of zeolite entities in the walls of the material is also clearly visible during the study by electron diffraction of the michronotropic sections with a thickness of the order of 70 nm on localized areas of the order of 100 nm. Nitrogen volumetric analysis combined with analysis by the α s method leads to a microporous volume V micro value of 0.3 ml / g (N 2 ), a mesoporous V meso volume value of 0, 6 ml / g (N 2 ) and a specific surface area of the final material of S = 680 m 2 / g. The macroporous mercury volume defined by mercury porosimetry is 0.5 ml / g (the value of the mesoporous mercury volume also obtained is in perfect agreement with the value obtained by volumetric nitrogen). The wide-angle XRD analysis leads to obtaining the diffractogram characteristic of the zeolite silicalite (size of the micropores, measured by XRD, of the order of 0.55 nm). An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
11,70 g d'une solution d'hydroxyde de tetraéthylammonium hydroxide (TEAOH 20% en masse dans une solution aqueuse) sont ajoutés à 7,8 g d'eau déminéralisée et 0,03 g d'hydroxyde de sodium NaOH. Le tout est laissé sous agitation pendant 10 minutes. 0,14 g de sec-butoxyde d'aluminium (Al(OsC4H9)3) sont alors introduits. Le tout est laissé sous agitation pendant 10 minutes. L'hydrolyse du précurseur aluminique est réalisée pendant 1 heure. 6 g de tétraéthylorthosilicate (TEOS) sont alors ajoutés. Le tout est maintenu sous agitation pendant 18 heures à température ambiante de manière à obtenir une solution limpide. 18 ml de cette solution sont alors ajoutés à une solution contenant 35,2 g d'éthanol, 11,3 g d'eau et 2 g de tensioactif F127 (pH du mélange = 10). Le rapport Vinorganique/Vorganique du mélange est égal à 0,17 et est calculé comme décrit ci-dessus. Le tout est laissé sous agitation pendant 10 minutes. L'ensemble est envoyé dans la chambre d'atomisation du générateur d'aérosol tel qu'il a été décrit dans la description ci-dessus et la solution est pulvérisée sous la forme de fines gouttelettes sous l'action du gaz vecteur (air sec) introduit sous pression (P = 1,5 bar). Les gouttelettes sont séchées selon le protocole décrit dans l'exposé de l'invention ci-dessus : elles sont acheminées via un mélange O2/N2 dans des tubes en PVC. Elles sont ensuite introduites dans un four réglé à une température de séchage fixée à 250°C. La poudre récoltée est alors séchée 12 heures à l'étuve à 95°C. 10 mg de poudre sont alors placés dans un autoclave de 100 ml (enceinte fermée susceptible de résister à des températures de l'ordre de 200°C et des pressions de l'ordre de 5 bars) en présence de 150 µl d'eau déminéralisée. L'autoclave est muni d'un système de "panier" ou de "cellule" permettant à la poudre de ne pas être en contact direct avec l'eau introduite tout en baignant dans la vapeur d'eau. L'autoclave est ensuite porté à une température de 95°C pendant 48 heures. La poudre récupérée est ensuite séchée à l'étuve à 95°C pendant 12 heures. La poudre est alors calcinée sous air pendant 5 h à 550°C. Le solide est caractérisé par DRX, par Volumétrie à l'azote, par porosimétrie au mercure, par MET, par MEB, par FX. L'analyse MET montre que les particules sphériques constitutives du matériau présentent une macroporosité de coeur caractérisée par des domaines de 300 à 500 nm de long et de 100 à 200 nm de large et une mésoporosité en périphérie des particules caractérisée par des domaines de 20 à 50 nm, l'ensemble étant caractéristique d'une séparation de phase organique - inorganique obtenue par un mécanisme de décomposition spinodale présente avant l'étape de calcination. La présence d'entités zéolithiques dans les parois du matériau est également clairement visible lors de l'étude par diffraction électronique des coupes michrotomées d'une épaisseur de l'ordre de 70 nm sur des zones localisées de l'ordre de 100 nm. L'analyse par volumétrie à l'azote combinée à l'analyse par la méthode αs conduit à une valeur du volume microporeux Vmicro de 0,35 ml/g (N2), une valeur du volume mésoporeux Vméso de 0,6 ml/g (N2) et une surface spécifique du matériau final de S = 700 m2/g. Le volume mercure macroporeux défini par porosimétrie au mercure est de 0,3 ml/g (la valeur du volume mercure mésoporeux également obtenue est en parfait accord avec la valeur obtenue par volumétrie à l'azote). L'analyse DRX aux grands angles conduit à l'obtention du diffractogramme caractéristique de la zéolithe bêta (taille des micopores, mesurée par DRX, de l'ordre de 0,66 nm). Le rapport molaire Si/Al obtenu par FX est de 50. Un cliché MEB des particules élémentaires sphériques ainsi obtenues indique que ces particules ont une taille caractérisée par un diamètre variant de 50 à 700 nm, la distribution en taille de ces particules étant centrée autour de 300 nm.11.70 g of a solution of tetraethylammonium hydroxide hydroxide (TEAOH 20% by weight in an aqueous solution) are added to 7.8 g of demineralized water and 0.03 g of sodium hydroxide NaOH. The whole is left stirring for 10 minutes. 0.14 g of aluminum sec-butoxide (Al (O s C 4 H 9 ) 3 ) are then introduced. The whole is left stirring for 10 minutes. The hydrolysis of the aluminum precursor is carried out for 1 hour. 6 g of tetraethylorthosilicate (TEOS) are then added. The whole is stirred for 18 hours at room temperature so as to obtain a clear solution. 18 ml of this solution are then added to a solution containing 35.2 g of ethanol, 11.3 g of water and 2 g of surfactant F127 (pH of the mixture = 10). The inorganic / organic V ratio of the mixture is 0.17 and is calculated as described above. The whole is left stirring for 10 minutes. The assembly is sent into the atomization chamber of the aerosol generator as described in the description above and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air ) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O 2 / N 2 mixture in PVC tubes. They are then introduced into an oven set at a drying temperature set at 250 ° C. The harvested powder is then dried for 12 hours in an oven at 95 ° C. 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C. and pressures of the order of 5 bars) in the presence of 150 μl of demineralised water . The autoclave is provided with a system of "basket" or "cell" allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor. The autoclave is then heated to a temperature of 95 ° C for 48 hours. The recovered powder is then dried in an oven at 95 ° C. for 12 hours. The powder is then calcined under air for 5 hours at 550 ° C. The solid is characterized by XRD, nitrogen volumetry, mercury porosimetry, TEM, SEM, FX. The TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the whole being characteristic of a phase separation organic - inorganic obtained by a spinodal decomposition mechanism present before the calcination step. The presence of zeolite entities in the walls of the material is also clearly visible during the study by electron diffraction of the michronotropic sections with a thickness of the order of 70 nm on localized areas of the order of 100 nm. Nitrogen volumetric analysis combined with analysis by the α s method leads to a microporous volume V micro value of 0.35 ml / g (N 2 ), a mesoporous V meso volume value of 0, 6 ml / g (N 2 ) and a specific surface area of the final material of S = 700 m 2 / g. The macroporous mercury volume defined by mercury porosimetry is 0.3 ml / g (the value of the mesoporous mercury volume also obtained is in perfect agreement with the value obtained by nitrogen volumetry). The wide-angle X-ray analysis leads to the characteristic diffractogram of zeolite beta (size of the micopores, measured by XRD, of the order of 0.66 nm). The molar Si / Al ratio obtained by FX is 50. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
0,41 g d'aluminate de sodium (NaAlO2) sont ajoutés à une solution contenant 0,17 g d'hydroxyde de sodium et 7,6 g d'eau déminéralisée. La solution est laissée sous agitation jusqu'à la dissolution du précurseur d'aluminium. 10 g de silicate de sodium (27% en poids en SiO2 et 14 % en NaOH) sont alors ajoutés sous vigoureuse agitation. Le tout est maintenu sous agitation pendant 18 heures à température ambiante de manière à obtenir une solution limpide. 15 ml de cette solution sont alors ajoutés à une solution contenant 35,2 g d'éthanol, 11,6 g d'eau et 6,3 g de tensioactif F127 (pH du mélange = 9,8). Le rapport Vinorganique/Vorganique du mélange est égal à 0,24 et est calculé comme décrit ci-dessus. Le tout est laissé sous agitation pendant 10 minutes. L'ensemble est envoyé dans la chambre d'atomisation du générateur d'aérosol tel qu'il a été décrit dans la description ci-dessus et la solution est pulvérisée sous la forme de fines gouttelettes sous l'action du gaz vecteur (air sec) introduit sous pression (P = 1,5 bar). Les gouttelettes sont séchées selon le protocole décrit dans l'exposé de l'invention ci-dessus : elles sont acheminées via un mélange O2/N2 dans des tubes en PVC. Elles sont ensuite introduites dans un four réglé à une température de séchage fixée à 250°C. La poudre récoltée est alors séchée 12 heures à l'étuve à 95°C. 10 mg de poudre sont alors placés dans un autoclave de 100 ml (enceinte fermée susceptible de résister à des températures de l'ordre de 200°C et des pressions de l'ordre de 5 bars) en présence de 150 µl d'eau déminéralisée. L'autoclave est muni d'un système de "panier" ou de "cellule" permettant à la poudre de ne pas être en contact direct avec l'eau introduite tout en baignant dans la vapeur d'eau. L'autoclave est ensuite porté à une température de 95°C pendant 48 heures. La poudre récupérée est ensuite séchée à l'étuve à 95°C pendant 12 heures. La poudre est alors calcinée sous air pendant 5 h à 550°C. Le solide est caractérisé par DRX et aux grands angles, par Volumétrie à l'azote, par porosimétrie au mercure, par MET, par MEB et par ICP, par FX. L'analyse MET montre que les particules sphériques constitutives du matériau présentent une macroporosité de coeur caractérisée par des domaines de 300 à 500 nm de long et de 100 à 200 nm de large et une mésoporosité en périphérie des particules caractérisée par des domaines de 20 à 50 nm, l'ensemble étant caractéristique d'une séparation de phase organique - inorganique obtenue par un mécanisme de décomposition spinodale présente avant l'étape de calcination. La présence d'entités zéolithiques dans les parois du matériau est également clairement visible lors de l'étude par diffraction électronique des coupes michrotomées d'une épaisseur de l'ordre de 70 nm sur des zones localisées de l'ordre de 100 nm. L'analyse par volumétrie à l'azote combinée à l'analyse par la méthode αs conduit à une valeur du volume microporeux Vmicro de 0,33 ml/g (N2), une valeur du volume mésoporeux Vméso de 0,8 ml/g (N2) et une surface spécifique du matériau final de S = 720 m2/g. Le volume mercure macroporeux défini par porosimétrie au mercure est de 0,5 ml/g (la valeur du volume mercure mésoporeux également obtenue est en parfait accord avec la valeur obtenue par volumétrie à l'azote). L'analyse DRX aux grands angles conduit à l'obtention du diffractogramme caractéristique de la zéolithe Y (taille des micopores, mesurée par DRX, de l'ordre de 0,8 nm). Le rapport molaire Si/Al obtenu par FX est de 8. Un cliché MEB des particules élémentaires sphériques ainsi obtenues indique que ces particules ont une taille caractérisée par un diamètre variant de 50 à 700 nm, la distribution en taille de ces particules étant centrée autour de 300 nm.0.41 g of sodium aluminate (NaAlO 2 ) are added to a solution containing 0.17 g of sodium hydroxide and 7.6 g of demineralized water. The solution is stirred until the aluminum precursor is dissolved. 10 g of sodium silicate (27% by weight of SiO 2 and 14% of NaOH) are then added with vigorous stirring. The whole is stirred for 18 hours at room temperature so as to obtain a clear solution. 15 ml of this solution are then added to a solution containing 35.2 g of ethanol, 11.6 g of water and 6.3 g of surfactant F127 (pH of the mixture = 9.8). The inorganic / organic V ratio of the mixture is 0.24 and is calculated as described above. The whole is left stirring for 10 minutes. The assembly is sent into the atomization chamber of the aerosol generator as described in the description above and the solution is sprayed in the form of fine droplets under the action of the carrier gas (dry air ) introduced under pressure (P = 1.5 bar). The droplets are dried according to the protocol described in the disclosure of the invention above: they are conveyed via an O 2 / N 2 mixture in PVC tubes. They are then introduced into an oven set at a temperature drying time set at 250 ° C. The harvested powder is then dried for 12 hours in an oven at 95 ° C. 10 mg of powder are then placed in a 100 ml autoclave (closed chamber capable of withstanding temperatures of the order of 200 ° C. and pressures of the order of 5 bars) in the presence of 150 μl of demineralised water . The autoclave is provided with a system of "basket" or "cell" allowing the powder not to be in direct contact with the water introduced while bathing in the water vapor. The autoclave is then heated to a temperature of 95 ° C for 48 hours. The recovered powder is then dried in an oven at 95 ° C. for 12 hours. The powder is then calcined under air for 5 hours at 550 ° C. The solid is characterized by XRD and at large angles, by nitrogen volumetry, by mercury porosimetry, by TEM, by SEM and by ICP, by FX. The TEM analysis shows that the spherical constitutive particles of the material have a core macroporosity characterized by domains 300 to 500 nm long and 100 to 200 nm wide and a mesoporosity at the periphery of the particles characterized by domains of 20 to 50 nm, the set being characteristic of an organic-inorganic phase separation obtained by a spinodal decomposition mechanism present before the calcination step. The presence of zeolite entities in the walls of the material is also clearly visible during the study by electron diffraction of the michronotropic sections with a thickness of the order of 70 nm on localized areas of the order of 100 nm. The analysis by nitrogen volumetric analysis combined with the α s method leads to a value of the micropore volume V micro of 0.33 ml / g (N 2), a value of the mesopore volume V meso 0, 8 ml / g (N 2 ) and a specific surface area of the final material of S = 720 m 2 / g. The macroporous mercury volume defined by mercury porosimetry is 0.5 ml / g (the value of the mesoporous mercury volume also obtained is in perfect agreement with the value obtained by volumetric nitrogen). The wide-angle XRD analysis leads to obtaining the diffractogram characteristic of zeolite Y (size of the micopores, measured by XRD, of the order of 0.8 nm). The Si / Al molar ratio obtained by FX is 8. An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 50 to 700 nm, the size distribution of these particles being centered around 300 nm.
Claims (19)
- A hierarchical porosity material consisting of at least two elementary spherical particles having a maximum diameter of 200 microns, at least one of said spherical particles comprises at least one matrix based on silicon oxide and exhibiting crystallized walls, said material having a macropore volume measured by mercury porosimetry ranging between 0.05 and 1 ml/g, a mesopore volume measured by nitrogen volumetric analysis ranging between 0.01 and 1 ml/g and a micropore volume measured by nitrogen volumetric analysis ranging between 0.03 and 0.4 ml/g.
- A material as claimed in claim 1, such that the macropore volume measured by mercury porosimetry ranges between 0.1 and 0.3 ml/g.
- A material as claimed in claim 1 or 2, such that the mesopore volume measured by nitrogen volumetric analysis ranges between 0.1 and 0.6 ml/g.
- A material as claimed in any one of claims 1 to 3, such that macroporosity is present in domains ranging between 50 and 1000 nm.
- A material as claimed in any one of claims 1 to 4, such that mesoporosity is present in domains ranging between 2 and 50 nm.
- A material as claimed in any one of claims 1 to 5, such that it exhibits mesoporosity-free elementary spherical particles.
- A material as claimed in any one of claims 1 to 6, such that said matrix has crystallized walls consisting of zeolitic entities.
- A material as claimed in claim 7, such that said zeolitic entities comprise at least one zeolite selected from among the zeolites of MFI, BEA, FAU and LTA structural type.
- A material as claimed in any one of claims 1 to 8, such that said matrix based on silicon oxide is entirely silicic.
- A material as claimed in any one of claims 1 to 8, such that said matrix based on silicon oxide comprises at least one element X selected from among aluminium, iron, boron, indium and gallium.
- A material as claimed in claim 10, such that element X is aluminium.
- A material as claimed in any one of claims 1 to 11, such that said elementary spherical particles have a diameter ranging between 50 nm and 10 microns.
- A material as claimed in any one of claims 1 to 12, such that it has a specific surface area ranging between 100 and 1100 m2/g.
- A method of preparing a material as claimed in any one of claims 1 to 13, comprising: a) preparing a clear solution containing the zeolitic entity precursor elements, i.e. at least one structuring agent, at least one silicic precursor and possibly at least one precursor of at least one element X selected from among aluminium, iron, boron, indium and gallium ; b) mixing into a solution at least one surfactant and at least said clear solution obtained in stage a), the surfactant initial concentration being lower than the critical micellar concentration and the variation of the free enthalpy of mixing ΔGm as well as the second derivative of the free enthalpy ∂2G/∂2x being greater than 0; c) aerosol atomizing said solution obtained in stage b) so as to lead to the formation of spherical droplets ; d) drying said droplets ; e) autoclaving the particles obtained in stage d) ; f) drying said particles obtained in stage e) ; and g) eliminating said structuring agent and said surfactant so as to obtain a hierarchical porosity crystallized material in the microporosity, mesoporosity and macroporosity range.
- A method as claimed in claim 14, such that element X is aluminium.
- A method as claimed in claim 14 or 15, such that said surfactant is a three-block copolymer, each block consisting of a poly(alkylene oxide) chain.
- A method as claimed in claim 16, such that said three-block copolymer consists of two poly(ethylene oxide) chains and of one poly(propylene oxide) chain.
- An adsorbent comprising the hierarchical porosity material as claimed in any one of claims 1 to 13 or prepared according to the method as claimed in any one of claims 14 to 17.
- A catalyst comprising the hierarchical porosity material as claimed in any one of claims 1 to 13 or prepared according to the method as claimed in any one of claims 14 to 17.
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FR2969513B1 (en) | 2010-12-22 | 2013-04-12 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A SPHERICAL MATERIAL HIERARCHISED POROSITY COMPRISING METALLIC PARTICLES PIEGEES IN A MESOSTRUCTURED MATRIX |
US10286391B2 (en) * | 2012-02-17 | 2019-05-14 | Inaeris Technologies, Llc | Catalyst system having meso and macro hierarchical pore structure |
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EP2197794A2 (en) | 2010-06-23 |
FR2920758B1 (en) | 2009-11-13 |
JP2010537940A (en) | 2010-12-09 |
CN101795970A (en) | 2010-08-04 |
FR2920758A1 (en) | 2009-03-13 |
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